JPS63172703A - Continuous sulfonation of polystyrene - Google Patents
Continuous sulfonation of polystyreneInfo
- Publication number
- JPS63172703A JPS63172703A JP286087A JP286087A JPS63172703A JP S63172703 A JPS63172703 A JP S63172703A JP 286087 A JP286087 A JP 286087A JP 286087 A JP286087 A JP 286087A JP S63172703 A JPS63172703 A JP S63172703A
- Authority
- JP
- Japan
- Prior art keywords
- polystyrene
- raw material
- reactor
- material solution
- sulfonating agent
- 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
- 238000006277 sulfonation reaction Methods 0.000 title claims abstract description 23
- 239000004793 Polystyrene Substances 0.000 title claims description 36
- 229920002223 polystyrene Polymers 0.000 title claims description 36
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 239000000470 constituent Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 17
- 150000008282 halocarbons Chemical class 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 229920001467 poly(styrenesulfonates) Polymers 0.000 abstract description 6
- 229960002796 polystyrene sulfonate Drugs 0.000 abstract description 4
- 239000011970 polystyrene sulfonate Substances 0.000 abstract description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 abstract 1
- 238000010008 shearing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 101100474383 Escherichia coli (strain K12) rpsO gene Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- -1 aliphatic halogenated hydrocarbon Chemical class 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
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] [Field of Industrial Application] The present invention produces a highly pure water-soluble polystyrene sulfonated product in high yield with few by-products and without the use of additives such as crosslinking inhibitors. It relates to a manufacturing method.
Ｃ従来の技術〕
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
コールの単独又ハ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Ｎａ
Ｃβ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
内に一８０２−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５０−３３８３８号及び特公昭５１−３
７２２６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５
１−３７２２７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。C. Prior Art] Various methods have been proposed for sulfonating polystyrene. For example, when polystyrene is sulfonated using chlorosulfonic acid in a chlorinated hydrocarbon, a specific amount of water, sulfuric acid, hydrochloric acid, methyl alcohol, or ethyl alcohol is added per monomer, either alone or in combination. -33838), during sulfonation,
Anionic compounds such as polystyrene sulfonate and/or
Alternatively, a method of adding a nonionic compound such as methyl cellulose (Japanese Patent Publication No. 51-37226), and a method of adding a hydrogen halide compound of a Lewis base (for example, Na
For example, a method of adding an alkali halide such as Cβ (Japanese Patent Publication No. 37227/1983). All of these methods prevent the formation of -802- crosslinks between or within polystyrene molecules during sulfonation, produce a water-soluble polystyrene sulfonated product with a small amount of by-products, and in high yield. The purpose is to obtain. However, Special Publication No. 50-33838 and Special Publication No. 51-3
In the method described in No. 7226, since water is present in the reaction system, it forms a heterogeneous system with the halogenated hydrocarbon solvent, and it is difficult to uniformly disperse water and maintain a more uniform system. There is a problem in that the amount of sulfonating agent required increases because water reacts with the sulfonating agent. On the other hand, the Tokuko Sho 5
The method of No. 1-37227 has the problem that it is not efficient as an industrial process because an inorganic salt is added and must be separated after the reaction is completed. Furthermore, all of the above methods are still insufficient in terms of prevention of intermolecular and intramolecular crosslinking, yield, etc., and there is a problem that the quality of the products varies widely, especially on an industrial scale. .
これに対して、本発明者らは、平均分子量が２００〜５
０．０００のポリスチレンをハロゲン化炭化水素溶媒中
でスルホン化するに際し、次の条件（１）及び（■）：
Ｑ、 １＜ ｄ ＜β〈０．７ ・・・（
１）４ ＜Ｑ／Ｖ＜４００ ・・・（Ｉ
Ｉ）（式中、ｄは攪拌羽根径’、ｍ〕、ｉは混合反応室
代表径Ｃ，ｍ）、Ｑは攪拌機の吐出量〔ｍ３／分〕■は
混合反応室内液量３ＩＴ１３〕、Ｑ／■は循環数口１／
分〕を示す。）
を満す攪拌機を用い、剪断力〔Ｎ／Ｃｌ１１〕が０．０
８〜１．５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 found that the average molecular weight was 200 to 5.
When sulfonating 0.000% polystyrene in a halogenated hydrocarbon solvent, the following conditions (1) and (■): Q, 1<d<β<0.7...(
1) 4 <Q/V<400...(I
I) (where d is the stirring blade diameter', m], i is the representative diameter of the mixing reaction chamber C, m), Q is the discharge rate of the stirrer [m3/min], ■ is the amount of liquid in the mixing reaction chamber 3IT13], Q /■ is a circulation number 1/
minutes]. ) with a shear force [N/Cl11] of 0.0.
We developed a method for sulfonating polystyrene characterized by reacting a sulfonating agent with polystyrene under conditions in the range of 8 to 1.5, and filed a patent application (Japanese Patent Application No. 1983
-25269). Although this method produces a highly purified water-soluble polystyrene sulfonated product in high yield with fewer by-products than conventional techniques, a better method for continuous sulfonation 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 produces fewer by-products than conventional techniques;
An object of the present invention is to provide a sulfonation method capable of producing a highly pure water-soluble polystyrene sulfonated product in high yield without using a crosslinking inhibitor or the like. Furthermore, the present invention aims to provide a simple continuous sulfonation method that 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 with a specific concentration and a specific amount of a sulfonating agent as a raw material solution, and performs a reaction by supplying the raw material solution and the sulfonating agent to a reactor at a rate that satisfies specific conditions. This was done based on the knowledge that the above problems could be effectively solved by doing so.
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〔工〕 ：
（式中、■１ は反応器へのスルホン化剤の導入線速度
〔Ｃａ ／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, in the present invention, when carrying out a sulfonation reaction by separately and continuously supplying a raw material solution in which polystyrene is dissolved and a sulfonating agent to a sulfonation reactor, 100 parts by weight of a halogenated hydrocarbon is used as a raw material solution. 1 to 100 parts by weight of polystyrene with an average molecular weight of 200 to 50,000 is dissolved in SO3 as a sulfonating agent.
0.7 to 2.0 per constituent monomer unit of polystyrene
(molar ratio), and the raw material solution and the sulfonating agent are expressed by the formula: The linear velocity of introduction of the raw material solution into the reactor and A indicate the amount of solvent (weight ratio) per 1 part by weight of polystyrene contained in the raw material solution. ) Provides a method for continuous sulfonation of polystyrene, characterized by supplying the polystyrene to a reactor under the following conditions.
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 in the range 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. On the other hand, if the average molecular weight is less than 200, polymerization reactions occur simultaneously due to the presence of unreacted styrene monomer. This is because the amount of water-insoluble sulfonated substances 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、エチレンジプロミドなど
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。ここで、ポリスチレンの量が１
１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, a raw material solution is prepared by dissolving the polystyrene in a halogenated hydrocarbon solvent. 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 include those inert to sulfonating agents such as dichloroethane, 1,1.2.2-tetrachloroethane, chloroform, and ethylene dipromide. and,
Per 100 parts by weight of the halogenated hydrocarbon solvent, 1 to 100 parts by weight, preferably 20 to 40 parts by weight, of polystyrene is added and dissolved. Here, the amount of polystyrene is 1
If it is less than 1 part, the sulfonation reactor will become too large, while if it exceeds 100 parts by weight, it will take too long to dissolve the polystyrene, and the viscosity will increase during sulfonation, resulting in the formation of crosslinked products and heterogeneous reactions. .
本発明ではスルホン化剤としてＳ０３を用いる。In the present invention, S03 is used as the sulfonating agent.
すなわち、液状ＳＯ，、ガス状Ｓ０３、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５Ｏｓ
（希釈ガスＳｏ、）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Ｓ０３
（希釈液状Ｓ○３ ）を使用する。ここで、希釈ガスＳ
Ｏ３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Ｓ０３ とし
てはＳＯ１濃度が１〜５Ｑｗｔ％、好ましくは５〜ｌ
Ｑｗｔ％のものが用いられる。That is, liquid SO, gaseous S03, gaseous 5Os diluted with an inert gas such as nitrogen gas, dehumidified air, etc.
Liquid S03 dissolved and diluted with (diluent gas So,) and halogenated hydrocarbon (preferably one with 1 or 2 carbon atoms)
(Diluted liquid S○3) is used. Here, diluent gas S
The O3 to be used has an SO3 concentration of 1 to 12% by volume, preferably 3 to 4% by volume, and the diluted liquid S03 has an SO1 concentration of 1 to 5Qwt%, preferably 5 to 1% by volume.
Qwt% 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 has an SO3 content of 0.7 to 2.0 (mole ratio) per constituent monomer unit of polystyrene.
, preferably from 1.0 to 1.5, separately and continuously from the raw material solution to the sulfonation reactor.
ここで、本発明では上記式ＣＩ）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（ｃｇ！／ｓｅｃ ）を反応器に通ずる供給管
の口部断面積〔ＣＩＩＩ〕で割って得られる値〔ｃ！Ｉ
ｌ／ｓｅＣ〕である。本発明では、Ｖ、 Ｘ 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−等を用いて行われるが、それぞれの導入
線速度をＯ，ｌ ｃｍ ／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 meets the conditions of the above formula CI). The linear velocity is the value [c! I
l/secC]. In the present invention, V, X A /
V2 is set in the range of 10 to 1000, preferably 12 to 300, but if the value is less than 10 or exceeds 1000, the reaction may be insufficient and side reactions such as increased polystyrene crosslinking may occur. Put it away. The raw material solution and sulfonating agent can be supplied to the reactor using conventional means, such as pumps,
Although this is carried out using a turbo blower or the like, it is preferable that the linear velocity of each introduction is 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／ｃｒｌ）以上の攪拌器を備えたものを用い
るのがよい。尚、ここで攪拌器としてはインラインミキ
サーも含まれる。The sulfonation reactor for carrying out the above reaction has a shear force of 0.
．． It is preferable to use one equipped with a stirrer of 0.05 (N/crl) or higher. In addition, an in-line mixer is also included as a stirrer here.
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 to cause a sulfonation reaction. At this time, the reaction is preferably carried out at 10 to 80°C, preferably 20 to 40°C, so that the raw material solution does not react. The residence time in the container is preferably 1 to 60 minutes, preferably 5 to 40 minutes.
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−
２５２６９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 following the above conditions, it is possible to produce a highly pure water-soluble polystyrene sulfonated product in high yield with fewer by-products than in the past.
If the conditions of No. 25269 are adopted, even better effects 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，Ｋ ＯＨ，Ｃａ（ＯＨ）ａｕｇ （
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 according to the present invention is obtained from the reactor in a state dispersed in a solvent, and the solvent is separated by a conventional method to obtain NaOH, KOH, Ca(OH) aug (
After neutralization with an alkali such as OH) 2, a highly pure 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 employing simple means, polystyrene sulfonate with few by-products and high purity can be produced in high yield. Furthermore, the method of the present invention is extremely excellent as an industrial mass production process, and the solvent can be easily separated and 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 sulfonated product obtained by this method is widely used as an antistatic agent for paper, a water reducing agent for concrete, a dispersant, etc.
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 explained with reference to Examples.
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製した。又、スルホン
化剤としては液状無水硫酸ＳＯａ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攪拌機付きの
容器で反応槽の内径０．１０８ｍ、槽容量１．４ Ｘ
Ｉ Ｑ−’ｍ’を用いた。Various raw material solutions were prepared using polystyrene having an average molecular weight of 4.500 or 10.000 and 1,2-dichloroethane or methylene chloride as a solvent. Furthermore, liquid anhydrous sulfuric acid SOa was used as the sulfonating agent. These were supplied to a sulfonation reactor under the conditions shown in Table 1 to carry out a sulfonation reaction. The reactor is a container equipped with a turbine type stirrer, the inner diameter of the reaction tank is 0.108 m, and the tank capacity is 1.4
IQ-'m' was used.
原料溶液を供給する供給口の内径は２．７６Ｘ１０−″
２ｍ１スルホン化剤の供給口の内径は３Ｘ１０−３ｍ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％ＮａＯ
Ｈ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轟りのＳＯ３導入率である。The inner diameter of the supply port for supplying the raw material solution is 2.76X10-''
The inner diameter of the 2 ml sulfonating agent supply port was 3 x 10-3 m, and the reaction vessel had a cooling jacket so that the reaction temperature could be controlled. Then after sulfonation, the solvent was separated and 20% NaO
The mixture was neutralized by adding H aqueous solution to obtain sodium polystyrene sulfonate. The results are summarized in Table-1. In addition, in the table, the yield of water-soluble sodium polystyrene sulfonate is
The sulfone group introduction rate is the SO3 introduction rate of the styrene monomer units constituting polystyrene.
Claims (1)
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２００〜５０，０
００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ＳＯ＿３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 〕： １０≦（Ｖ＿１／Ｖ＿２）×Ａ≦１，０００・・・〔
I 〕（式中、Ｖ＿１は反応器へのスルホン化剤の導入線
速度〔Ｃ＿ｍ／ｓ〕、Ｖ＿２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。[Claims] When carrying out a sulfonation reaction by separately and continuously feeding a raw material solution in which polystyrene is dissolved and a sulfonating agent to a sulfonation reactor, 100 parts by weight of halogenated hydrocarbon is used as the raw material solution. per unit, average molecular weight is 200 to 50,0
00 polystyrene dissolved in 1 to 100 parts by weight, SO_3 is used as the sulfonating agent in an amount of 0.7 to 2.0 (mole ratio) per constituent monomer unit of the polystyrene, and the raw material solution and the sulfonating agent and the formula [I]: 10≦(V_1/V_2)×A≦1,000...[
I] (where, V_1 is the linear velocity of 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 polystyrene 1 contained in the raw material solution.
The amount of solvent per part by weight (weight ratio) is shown. ) A method for continuous sulfonation of polystyrene, characterized in that polystyrene is supplied to a reactor under the following conditions.
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 true JPS63172703A (en) | 1988-07-16 |
| JPH0751608B2 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) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2631018A1 (en) * | 1988-05-04 | 1989-11-10 | Dow Chemical Co | APPARATUS AND PROCESS FOR PRODUCING SULFURIC ANHYDRIDE AS A REAGENT FOR SULFONATING SURFACES OF POLYMER 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
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2631018A1 (en) * | 1988-05-04 | 1989-11-10 | Dow Chemical Co | APPARATUS AND PROCESS FOR PRODUCING SULFURIC ANHYDRIDE AS A REAGENT FOR SULFONATING SURFACES OF POLYMER 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0751608B2 (en) | 1995-06-05 |
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| LAPS | Cancellation because of no payment of annual fees |