JPH0751608B2 - Method for continuous sulfonation of polystyrene - Google Patents
Method for continuous sulfonation of polystyreneInfo
- Publication number
- JPH0751608B2 JPH0751608B2 JP286087A JP286087A JPH0751608B2 JP H0751608 B2 JPH0751608 B2 JP H0751608B2 JP 286087 A JP286087 A JP 286087A JP 286087 A JP286087 A JP 286087A JP H0751608 B2 JPH0751608 B2 JP H0751608B2
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- JP
- Japan
- Prior art keywords
- polystyrene
- raw material
- sulfonation
- material solution
- reactor
- Prior art date
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、副生物が少なく、架橋防止剤等の添加剤を使
用しなくても純度の高い水溶性のポリスチレンスルホン
化物を高収率で製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention provides a highly pure water-soluble polystyrene sulfonate in a high yield with little by-products and without using additives such as a crosslinking inhibitor. The present invention relates to a manufacturing method.
これまでにポリスチレンのスルホン化方法として種々の
方法が提案されている。例えば、塩素化炭化水素中でク
ロルスルホン酸を用いてポリスチレンをスルホン化する
際に、水、硫酸、塩酸、メチルアルコール、エチルアル
コールの単独又は併用をモノマー当り特定量添加する方
法（特公昭50−33838号）、スルホン化の際に、ポリス
チレンスルホン酸塩等の陰イオン系化合物及び／又はメ
チルセルロース等の非イオン系化合物を添加する方法
（特公昭51−37226号）、及びスルホン化の際にルイス
塩基のハロゲン化水素塩化合物（例えばNaCl等のハロゲ
ン化アルカリ）を添加する方法（特公昭51−37227号）
などである。これらの方法は、いずれもスルホン化に際
し、ポリスチレン分子間又は分子内に−SO2−による架
橋が生成するのを防止し、副生物の量が少なく、かつ高
収率で水溶性のポリスチレンスルホン化物を得ることを
目的とするものである。しかしながら、特公昭50−3383
8号及び特公昭51−37226号に記載された方法は反応系中
に水が存在するため、ハロゲン化炭化水素溶媒と不均一
系を形成し、水を均一に分散させて、より均一な系に保
つのがむずかしく、又水がスルホン化剤と反応するため
にスルホン化剤の必要量が多くなるという問題がある。
一方、特公昭51−37227号の方法では、無機塩を添加す
るので反応終了後に分離する必要があり工業的プロセス
としては効率的でないといった問題がある。さらに上記
の方法はいずれも、分子間、分子内架橋の防止について
も、収率等の点においても未だ不十分であり、特に工業
化スケールにおいては生成物の品質のふれが大きいとい
う問題があった。Various methods have been proposed so far as methods for sulfonation of polystyrene. For example, a method of adding a specific amount of water, sulfuric acid, hydrochloric acid, methyl alcohol or ethyl alcohol alone or in combination per monomer when sulfonating polystyrene with chlorosulfonic acid in a chlorinated hydrocarbon (JP-B-50- 33838), a method of adding an anionic compound such as polystyrene sulfonate and / or a nonionic compound such as methylcellulose during sulfonation (JP-B-51-37226), and Lewis during sulfonation. Method of adding a hydrogen halide compound of a base (for example, alkali halide such as NaCl) (Japanese Patent Publication No. 51-37227)
And so on. All of these methods prevent the formation of cross-links due to -SO 2- between polystyrene molecules during or during sulfonation, the amount of by-products is small, and the yield of the water-soluble polystyrene sulfonate is high. The purpose is to obtain. However, Japanese Examined Patent Publication No. 50-3383
Since the method described in No. 8 and Japanese Patent Publication No. 51-37226 has water in the reaction system, it forms a heterogeneous system with a halogenated hydrocarbon solvent and uniformly disperses the water to obtain a more uniform system. However, there is a problem that the amount of sulfonating agent required is large because water reacts with the sulfonating agent.
On the other hand, the method of JP-B-51-37227 has a problem that it is not efficient as an industrial process because it needs to be separated after the reaction because an inorganic salt is added. Furthermore, all of the above methods are still insufficient in terms of prevention of intermolecular and intramolecular cross-linking, and also in terms of yield, etc., and there is a problem that the quality of the product largely fluctuates particularly on an industrial scale. .
これに対して、本発明者らは、平均分子量が200〜50,00
0のポリスチレンをハロゲン化炭化水素溶媒中でスルホ
ン化するに際し、次の条件（Ｉ）及び（II）： 0.1＜ｄ＜ｌ＜0.7 ・・・（Ｉ） ４＜Q/V＜400 ・・・（II） （式中、ｄは撹拌羽根径〔ｍ〕、ｌは混合反応室代表径
〔ｍ〕、Ｑは撹拌機の吐出量〔m3/分〕 Ｖは混合反応室内液量〔m3〕、Q/Vは循環数〔1/分〕を
示す。） を満す撹拌機を用い、剪断力〔N/cm2〕が0.08〜1.5の範
囲となる条件下で、スルホン化剤とポリスチレンとを反
応させることを特徴とするポリスチレンのスルホン化方
法を開発し、特許出願した（特願昭61−25269号）。こ
の方法は、従来技術に比べて副生物が少なく純度の高い
水溶性ポリスチレンスルホン化物を高収率で製造できる
ものであるが、よりすぐれたポリスチレンの連続スルホ
ン化方法が望まれている。On the other hand, the present inventors have found that the average molecular weight is 200 to 50,00.
In sulfonation of polystyrene of 0 in a halogenated hydrocarbon solvent, the following conditions (I) and (II): 0.1 <d <l <0.7 (I) 4 <Q / V <400 ... (II) (In the formula, d is the diameter of the stirring blade [m], l is the representative diameter of the mixing reaction chamber [m], Q is the discharge rate of the stirrer [m 3 / min] V is the amount of liquid in the mixing reaction chamber [m 3] ], Q / V indicates the circulation number [1 / min].) Using a stirrer satisfying the following conditions, the shearing force [N / cm 2 ] is in the range of 0.08 to 1.5, and the sulfonating agent and polystyrene are used. A method for sulfonation of polystyrene, which is characterized by reacting with, was developed and a patent application was filed (Japanese Patent Application No. 61-25269). This method is capable of producing a high-purity water-soluble polystyrene sulfonate with less by-products as compared with the prior art, but a superior continuous sulfonation method of polystyrene is desired.
従って、本発明は、従来の技術よりも副生物が少なく、
架橋防止剤等を使用しなくとも純度の高い水溶性ポリス
チレンスルホン化物を高収率で製造することができるス
ルホン化方法を提供することを目的とする。さらに、本
発明は、工業的な大量生産プロセスとして利用可能な簡
単な連続スルホン化方法を提供することを目的とする。Therefore, the present invention has fewer by-products than the prior art,
An object of the present invention is to provide a sulfonation method capable of producing a highly pure water-soluble polystyrene sulfonate in a high yield without using a crosslinking inhibitor or the like. Further, the present invention aims to provide a simple continuous sulfonation method which can be used as an industrial mass production process.
本発明は、原料溶液として特定濃度のポリスチレン溶液
及び特定量のスルホン化剤を用い、かつ反応器への該原
料溶液とスルホン化剤とを特定の条件を満す速度で供給
して反応を行わせると上記問題点を有効に解決できると
の知見に基づいてなされたのである。The present invention uses a polystyrene solution having a specific concentration and a specific amount of a sulfonating agent as a raw material solution, and performs the reaction by supplying the raw material solution and the sulfonating agent to a reactor at a rate satisfying specific conditions. This was done based on the finding that the above problems can be effectively solved.
すなわち、本発明は、ポリスチレンを溶解した原料溶液
とスルホン化剤とを別々に、かつ連続的にスルホン化反
応器に供給してスルホン化反応を行うに際し、原料溶液
としてハロゲン化炭化水素100重量部当り、平均分子量
が200〜50,000のポリスチレン１〜100重量部を溶解した
ものを用い、スルホン化剤としてSO3をポリスチレンの
構成モノマー単位当り0.7〜2.0（モル比）の量で用い、
かつ原料溶液とスルホン化剤とを、式〔Ｉ〕： （式中、V1は反応器へのスルホン化剤の導入線速度〔Cm
/s〕、V2は反応器への原料溶液の導入線速度及びＡは原
料溶液中に含まれるポリスチレン１重量部当りの溶媒量
（重量比）を示す。） の条件で反応器に供給することを特徴とするポリスチレ
ンの連続スルホン化方法を提供する。That is, the present invention, a raw material solution in which polystyrene is dissolved and a sulfonating agent are separately and continuously supplied to a sulfonation reactor to perform a sulfonation reaction, and 100 parts by weight of a halogenated hydrocarbon as a raw material solution. Per 1 to 100 parts by weight of polystyrene having an average molecular weight of 200 to 50,000 is dissolved, SO 3 is used as a sulfonating agent in an amount of 0.7 to 2.0 (molar ratio) per monomer unit constituting polystyrene,
And the raw material solution and the sulfonating agent are represented by the formula [I]: (In the formula, V 1 is the linear velocity of the introduction of the sulfonating agent into the reactor [C m
/ s], V 2 is the linear velocity of introduction of the raw material solution into the reactor, and A is the amount of solvent (weight ratio) per 1 part by weight of polystyrene contained in the raw material solution. ) The method for continuous sulfonation of polystyrene, characterized in that it is fed to the reactor under the conditions of
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
に溶解させて原料溶液を調製する。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
化剤に不活性のものが例示される。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。ここで、ポリスチレンの量が１重量部未満ではスル
ホン化反応器が大きくなりすぎ、一方100重量部を越え
るとポリスチレンの溶解に時間がかかりすぎるととも
に、スルホン化時に粘度が上昇し、架橋物の生成や不均
一反応が生じてしまう。In the present invention, the above-mentioned polystyrene is dissolved in a halogenated hydrocarbon solvent to prepare a raw material solution. 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- Examples thereof include those which are inactive to sulfonating agents such as dichloroethane, 1,1,2,2-tetrachloroethane, chloroform and ethylene dibromide. And, the polystyrene is added in an amount of 1 to 100 per 100 parts by weight of the halogenated hydrocarbon solvent.
Parts by weight, preferably 20-40 parts by weight are added and dissolved. Here, if the amount of polystyrene is less than 1 part by weight, the sulfonation reactor becomes too large, while if it exceeds 100 parts by weight, it takes too long to dissolve the polystyrene, and the viscosity increases during sulfonation, resulting in the formation of crosslinked products. Or a heterogeneous reaction occurs.
本発明ではスルホン化剤としてSO3を用いる。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１〜50wt％、好ましくは５〜10
wt％のものが用いられる。In the present invention, SO 3 is used as the sulfonating agent. That is, liquid SO 3, gaseous SO 3, for example, gaseous SO 3 (diluting gas SO 3) diluted such an inert gas or dehumidified air such as nitrogen gas
And liquid SO 3 (diluted liquid SO 3 ) dissolved and diluted with 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%, SO 3 concentration is 1 to 50 wt% as dilution liquid SO 3, preferably 5 ~Ten
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となるような割合で、原料溶液とは別々
に、かつ連続的にスルホン化反応器に供給する。In the present invention, the sulfonating agent is continuously and separately from the raw material solution at a ratio such that SO 3 is 0.7 to 2.0 (molar ratio), preferably 1.0 to 1.5 per monomer unit constituting polystyrene. To the sulfonation reactor.
ここで、本発明では上記式〔Ｉ〕の条件に合致した線速
度で原料溶液とスルホン化剤とを反応器に供給すること
を特徴とするものである。尚、線速度は、単位秒あたり
の供給量〔cm3/sec〕を反応器に通ずる供給管の口部断
面積〔cm2〕で割って得られる値〔cm/sec〕である。本
発明では、V1×A/V2を10〜1000、好ましくは12〜300の
範囲とするが、該値が10未満でも、又1000を越えても、
反応が不十分となりポリスチレン架橋物が増加したり等
副反応が増加してしまう。尚、反応器への原料溶液、ス
ルホン化剤の供給は通常の手段、例えばポンプ、ターボ
ブロワー等を用いて行われるが、それぞれの導入線速度
を0.1cm/sec以上とするのがよい。Here, the present invention is characterized in that the raw material solution and the sulfonating agent are supplied to the reactor at a linear velocity that matches the condition of the above formula [I]. The linear velocity is a value [cm / sec] obtained by dividing the supply rate [cm 3 / sec] per unit second by the cross-sectional area [cm 2 ] of the mouth of the supply pipe leading to the reactor. In the present invention, V 1 × A / V 2 is in the range of 10 to 1000, preferably 12 to 300, but even if the value is less than 10 or more than 1000,
The reaction becomes insufficient and cross-linked polystyrene increases and side reactions increase. The raw material solution and the sulfonating agent are supplied to the reactor by an ordinary means such as a pump or a turbo blower, and the introduction linear velocity of each is preferably 0.1 cm / sec or more.
上記反応を行うスルホン化反応器としては、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
い。尚、ここで撹拌器としてはインラインミキサーも含
まれる。As a sulfonation reactor for performing the above reaction, the shearing force is 0.
It is recommended to use one equipped with a stirrer of 05 (N / cm 2 ) or more. In addition, an in-line mixer is also included as the stirrer.
スルホン化反応器においては、原料溶液とスルホン化剤
とが接触してスルホン化反応が生じるが、この際反応を
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分とするのがよい。In the sulfonation reactor, the raw material solution and the sulfonating agent come into contact with each other to cause a sulfonation reaction.
It is good to carry out at 10 to 80 ° C, preferably 20 to 40 ° C, and the time for which the raw material solution stays in the reactor is 1 to 60 minutes, preferably 5 to
40 minutes is recommended.
本発明では上記条件に従うことによって、従来よりも副
生物が少なく、純度の高い水溶性ポリスチレンスルホン
化物を高収率で製造できるが、さらに上記特願昭61−25
269号の条件を採用すると、一層すぐれた効果が得られ
る。In the present invention, by complying with the above conditions, a water-soluble polystyrene sulfonate having less purity and higher purity than the conventional one can be produced in a high yield.
By adopting the conditions of No. 269, more excellent effect can be obtained.
本発明により製造されたポリスチレンスルホン酸は溶媒
に分散した状態で反応器から得られ、常法により溶媒を
分離し、NaOH、KOH、Ca（OH）２、Mg（OH）２等のアル
カリで中和後、高純度のポリスチレンスルホン酸塩が得
られる。The polystyrene sulfonic acid produced by the present invention is obtained from the reactor in a state of being dispersed in a solvent, the solvent is separated by a conventional method, and the medium is diluted with an alkali such as NaOH, KOH, Ca (OH) 2 and Mg (OH) 2. After soaking, a high-purity polystyrene sulfonate is obtained.
本発明によれば、簡易な手段を採用することにより、副
生物が少なく、かつ純度の高いポリスチレンスルホン酸
塩を高収率で製造できる。又、本発明の方法は工業的大
量生産プロセスとして極めてすぐれたものであり、溶媒
の分離も容易であって、該溶媒の再利用が可能である。According to the present invention, by adopting a simple means, it is possible to produce a high-purity polystyrene sulfonate with few by-products and high purity. In addition, the method of the present invention is extremely excellent as an industrial mass production process, the solvent can be easily separated, and the solvent can be reused.
従って、本方法により得られたポリスチレンスルホン化
物は、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, the polystyrene sulfonate obtained by this method is widely used as an antistatic agent for paper, a concrete water reducing agent, a dispersant, and the like.
次に実施例により本発明を具体的に説明する。Next, the present invention will be specifically described with reference to examples.
実施例１ 平均分子量4,500又は10,000のポリスチレン及び溶媒と
して、1,2−ジクロロエタン又は塩化メチレンを用いて
種々の原料溶液を調整した。又、スルホン化剤としては
液状無水硫酸SO3を用いた。これらを表−１に示す条件
でスルホン化反応器に供給してスルホン化反応を行っ
た。尚、反応器はタービン型撹拌機付きの容器で反応槽
の内径0.108m、槽容量1.4×10-3m3を用いた。原料溶液
を供給する供給口の内径は2.76×10-2m、スルホン化剤
の供給口の内径は３×10-3mであり、反応槽は冷却可能
なジャケットを有しており、反応温度をコントロールす
ることができる形態となっている。次いでスルホン化
後、溶媒を分離し、20％NaOH水溶液を加えて中和し、ポ
リスチレンスルホン酸ナトリウムを得た。結果をまとめ
て表−１に示す。尚、表中、水溶性ポリスチレンスルホ
ン酸ナトリウムの収率は、 から求め、スルホン基導入率はポリスチレンを構成する
スチレンモノマー単位当りのSO3導入率である。Example 1 Various raw material solutions were prepared by using polystyrene having an average molecular weight of 4,500 or 10,000 and 1,2-dichloroethane or methylene chloride as a solvent. Liquid anhydrous sulfuric acid SO 3 was used as the sulfonating agent. These were supplied to the sulfonation reactor under the conditions shown in Table 1 to carry out the sulfonation reaction. The reactor was a vessel equipped with a turbine-type stirrer, and the inner diameter of the reaction tank was 0.108 m and the tank capacity was 1.4 × 10 −3 m 3 . The inner diameter of the supply port for supplying the raw material solution is 2.76 × 10 -2 m, the inner diameter of the supply port for the sulfonating agent is 3 × 10 -3 m, the reaction tank has a jacket that can be cooled, and the reaction temperature is It is a form that can control. Then, after sulfonation, the solvent was separated, and a 20% aqueous NaOH solution was added for neutralization to obtain sodium polystyrene sulfonate. The results are summarized in Table-1. In the table, the yield of water-soluble sodium polystyrene sulfonate is The sulfo group introduction rate is the SO 3 introduction rate per styrene monomer unit constituting polystyrene.
実施例２ 実施例１で製造したポリスチレンスルホン酸塩を用い、
石炭−水スラリー用分散剤としての性能を評価した。 Example 2 Using the polystyrene sulfonate prepared in Example 1,
The performance as a dispersant for coal-water slurry was evaluated.
ステンレス鋼製ボールを充填率50％で収容する６リット
ル（内径19cm）のステンレス鋼製ボールミルに、スラリ
ーに対して0.4重量％（有効成分換算）の実施例１本発
明品No.5のポリスチレンスルホン酸Na、水465g及び粒系
3mm以下に粉砕したサクソンベール炭1000gを仕込んだ
後、65rpmで回転させ、レーザー回折型粒度分布計でス
ラリーの粒度（粒径74μｍ以下の粒子の数）を測定しな
がら、粒径74μｍ以下の粒子量が80％になるまで粉砕し
た。粉砕後、ボールミルからスラリーを取り出し、ホモ
ミキサーにより4000rpmで10分間かきまぜた後、スラリ
ーの粘度及び安定性を求めた。A 6 liter (inner diameter 19 cm) stainless steel ball mill containing stainless steel balls at a filling rate of 50% contained 0.4 wt% of the slurry (active ingredient conversion). Acid Na, water 465g and granules
After charging 1000 g of Saxon bale charcoal crushed to 3 mm or less, rotate it at 65 rpm and measure the particle size of the slurry (the number of particles with a particle size of 74 μm or less) with a laser diffraction type particle size distribution analyzer Grind until the amount was 80%. After crushing, the slurry was taken out from the ball mill and stirred with a homomixer at 4000 rpm for 10 minutes, and then the viscosity and stability of the slurry were determined.
その結果、スラリー粘度800cp、ふるい上の量11重量
％、硬さ○と良好であった。なお、スラリー粘度、安定
性の評価は以下の方法で行った。また、サクソンベール
炭の性状を表−２に示す。As a result, the slurry viscosity was 800 cp, the amount on the sieve was 11% by weight, and the hardness was good. The slurry viscosity and stability were evaluated by the following methods. Table 2 shows the properties of Saxon bale charcoal.
（１）粘度 ハーケの粘度計により、100sec-1down時の粘度を測定し
た。(1) Viscosity The viscosity at 100 sec -1 down was measured with a Haake viscometer.
（２） 250mlの広口ポリ瓶にスラリーを入れ、25℃で７日間静
置した後、16メッシュのふるい上にあけた際のふるい上
の量（スラリー全量に対する重量％）を求めるととも
に、ポリ瓶に残ったスラリーの硬さをスパチュラでかき
まぜた際の感触を次に示す基準で評価して、安定性を求
めた。(2) Put the slurry in a 250 ml wide-mouthed plastic bottle, leave it at 25 ° C for 7 days, and then determine the amount on the sieve (% by weight relative to the total amount of slurry) when opened on a 16-mesh sieve. Stability was determined by evaluating the feel of the slurry remaining in the above sample when stirred with a spatula according to the following criteria.
○：スラリーが柔らかい △：スラリーが硬い ×：スラリーが極めて硬い 実施例３ 実施例１本発明品No.5のポリスチレンスルホン酸Naをセ
メント重量に対して0.3％添加（有効成分換算）し、JIS
Ａ−6204に準拠してスランプ18cmのコンクリートを調
製して減水率を評価した。その結果、減水率は15.6％と
良好であった。○: Slurry is soft △: Slurry is hard ×: Slurry is extremely hard Example 3 Example 1 0.3% of Na polystyrene sulfonate of the present invention product No. 5 was added to the cement weight (effective component conversion), and JIS
A slump 18 cm concrete was prepared according to A-6204 to evaluate the water reduction rate. As a result, the water reduction rate was good at 15.6%.
Claims (1)
ン化剤とを別々に、かつ連続的にスルホン化反応器に供
給してスルホン化反応を行うに際し、原料溶液としてハ
ロゲン化炭化水素100重量部当り、平均分子量が200〜5
0,000のポリスチレン１〜100重量部を溶解したものを用
い、スルホン化剤としてSO3をポリスチレンの構成モノ
マー単位当り0.7〜2.0（モル比）の量で用い、かつ原料
溶液とスルホン化剤とを、式〔Ｉ〕： （式中、V1は反応器へのスルホン化剤の導入線速度〔Cm
/s〕、V2は反応器への原料溶液の導入線速度及びＡは原
料溶液中に含まれるポリスチレン１重量部当りの溶媒量
（重量比）を示す。） の条件で反応器に供給することを特徴とするポリスチレ
ンの連続スルホン化方法。1. A raw material solution in which polystyrene is dissolved and a sulfonating agent are separately and continuously supplied to a sulfonation reactor to carry out a sulfonation reaction, as a raw material solution per 100 parts by weight of a halogenated hydrocarbon. , The average molecular weight is 200-5
Using a solution of 1 to 100 parts by weight polystyrene 0,000, the SO 3 used in an amount per constituent monomer units of polystyrene 0.7-2.0 (molar ratio) as a sulfonating agent, and a raw material solution and a sulfonating agent, Formula [I]: (In the formula, V 1 is the linear velocity of the introduction of the sulfonating agent into the reactor [C m
/ s], V 2 is the linear velocity of introduction of the raw material solution into the reactor, and A is the amount of solvent (weight ratio) per 1 part by weight of polystyrene contained in the raw material solution. ) A method for continuous sulfonation of polystyrene, characterized in that it is fed to the reactor under the conditions of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP286087A JPH0751608B2 (en) | 1987-01-09 | 1987-01-09 | Method for continuous sulfonation of polystyrene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP286087A JPH0751608B2 (en) | 1987-01-09 | 1987-01-09 | Method for continuous sulfonation of polystyrene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63172703A JPS63172703A (en) | 1988-07-16 |
| JPH0751608B2 true JPH0751608B2 (en) | 1995-06-05 |
Family
ID=11541130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP286087A Expired - Fee Related JPH0751608B2 (en) | 1987-01-09 | 1987-01-09 | Method for continuous sulfonation of polystyrene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0751608B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0340617B1 (en) * | 1988-05-04 | 1995-03-29 | The Dow Chemical Company | Apparatus and process for the generation of sulfur trioxide reagent for sulfonation of the surface of polymeric resins |
| AU678732B2 (en) * | 1994-11-14 | 1997-06-05 | Lion Corporation | Coherent method for preparing water-soluble sulfonated polymer |
| AU2005237160B2 (en) * | 1998-01-12 | 2007-12-13 | Dexerials Corporation | Method of manufacturing polyelectrolyte |
-
1987
- 1987-01-09 JP JP286087A patent/JPH0751608B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63172703A (en) | 1988-07-16 |
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