JPH0742335B2 - Method for producing alkaline earth metal salt of polystyrene sulfonate - Google Patents
Method for producing alkaline earth metal salt of polystyrene sulfonateInfo
- Publication number
- JPH0742335B2 JPH0742335B2 JP1996187A JP1996187A JPH0742335B2 JP H0742335 B2 JPH0742335 B2 JP H0742335B2 JP 1996187 A JP1996187 A JP 1996187A JP 1996187 A JP1996187 A JP 1996187A JP H0742335 B2 JPH0742335 B2 JP H0742335B2
- Authority
- JP
- Japan
- Prior art keywords
- alkaline earth
- earth metal
- polystyrene
- neutralization
- sulfonic acid
- 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
- 229910052784 alkaline earth metal Inorganic materials 0.000 title claims description 13
- -1 alkaline earth metal salt Chemical class 0.000 title claims description 13
- 229920001467 poly(styrenesulfonates) Polymers 0.000 title claims description 10
- 229960002796 polystyrene sulfonate Drugs 0.000 title claims description 8
- 239000011970 polystyrene sulfonate Substances 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 22
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 14
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 14
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 12
- 239000004793 Polystyrene Substances 0.000 claims description 11
- 229920002223 polystyrene Polymers 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 150000008282 halocarbons Chemical class 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006277 sulfonation reaction Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000003809 water extraction Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
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〕 本発明はポリスチレンスルホン酸アルカリ土類金属塩の
製造法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing a polystyrene sulfonate alkaline earth metal salt.
従来からポリスチレンスルホン酸塩を製造する方法とし
ては、常法によりポリスチレンをスルホン化した後、該
スルホン化物を濾別し、これを水に溶解した後、アンモ
ニア水で中和する方法が知られている（特公昭51−3722
6号公報）。そして、該方法に準じて、水酸化ナトリウ
ムや水酸化カリウムを中和剤として用いて、それぞれポ
リスチレンスルホン酸ナトリウム及びカリウムが製造さ
れている。Conventionally, as a method for producing a polystyrene sulfonate, a method in which polystyrene is sulfonated by a conventional method, the sulfonated product is filtered off, dissolved in water, and then neutralized with aqueous ammonia is known. Yes (Japanese Patent Publication No. 51-3722)
No. 6). Then, according to this method, sodium polystyrene sulfonate and potassium polystyrene are produced using sodium hydroxide and potassium hydroxide as neutralizing agents, respectively.
これに対して、中和剤として水酸化カルシウムや水酸化
マグネシウム等のアルカリ土類金属水酸化物を用いて上
記反応を行うと種々の問題が生じる。例えば（ｉ）これ
らの水酸化物はの水に溶解しにくいので水性分散液とし
て使用するが、反応性が悪く中和反応時間が長くなって
しまう。（ii）中和反応時に反応液中に残存する未反応
SO3とアルカリ土類金属水酸化物とが反応して、水不溶
性のアルカリ土類金属硫酸塩が生成するので、該水溶性
塩中に未反応のアルカリ土類金属水酸化物が混入し、ア
ルカリ土類金属硫酸塩の分離効率が低下する。On the other hand, various problems occur when the above reaction is carried out using an alkaline earth metal hydroxide such as calcium hydroxide or magnesium hydroxide as a neutralizing agent. For example, (i) since these hydroxides are difficult to dissolve in water, they are used as an aqueous dispersion, but the reactivity is poor and the neutralization reaction time becomes long. (Ii) Unreacted remaining in the reaction solution during the neutralization reaction
SO 3 and the alkaline earth metal hydroxide react to form a water-insoluble alkaline earth metal sulfate, so unreacted alkaline earth metal hydroxide is mixed in the water-soluble salt, Separation efficiency of alkaline earth metal sulfate decreases.
従って、本発明は、中和時間を短縮でき、かつ副生する
アルカリ土類金属硫酸塩中にアルカリ土類金属水酸化物
の混入量が少なくて該硫酸塩を効率よく分離除去できる
ポリスチレンスルホン酸アルカリ土類金属塩の製造方法
を提供することを目的とする。Therefore, the present invention is a polystyrene sulfonic acid capable of shortening the neutralization time and efficiently separating and removing the alkaline earth metal hydroxide in the by-produced alkaline earth metal hydroxide with a small amount of the alkaline earth metal hydroxide mixed therein. It is an object to provide a method for producing an alkaline earth metal salt.
本発明は、スルホン化生成物から反応有機溶媒を分離し
て得たポリスチレンスルホン酸をアルカリ土類金属水酸
化物を含む水性分散液を用いて、特定の条件下で中和
し、次いで水酸化ナトリウム等のアルカリ金属水酸化物
で残存ポリスチレンスルホン酸を中和した後、アルカリ
土類金属硫酸塩を分離すると、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。In the present invention, polystyrene sulfonic acid obtained by separating a reaction organic solvent from a sulfonated product is neutralized under specific conditions using an aqueous dispersion containing an alkaline earth metal hydroxide, and then hydroxylated. It was made based on the finding that the above problems can be effectively solved by neutralizing the residual polystyrene sulfonic acid with an alkali metal hydroxide such as sodium and then separating the alkaline earth metal sulfate.
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該
溶媒を分離したポリスチレンスルホン酸を、アルカリ土
類金属水酸化物を含む水性分散液を用いて、次の条件
（Ｉ）及び（II）： Ａ６ ……（Ｉ） ４B/A10 ……（II） （式中、Ａは中和後のポリスチレンスルホン酸塩溶液の
pHであり、Ｂは中和に要する時間（分）を示す。） を満す条件で中和し、次いで中和溶液中に残存するポリ
スチレンスルホン酸をアルカリ金属水酸化物で中和した
後、該水溶液中のアルカリ土類金属硫酸塩を分離するこ
とを特徴とするポリスチレンアルカリ土類金属塩の製造
方法を提供する。That is, the present invention, polystyrene sulfonic acid having an average molecular weight of 200 to 50,000 is sulfonated polystyrene in a halogenated hydrocarbon solvent, the solvent is separated, using an aqueous dispersion containing an alkaline earth metal hydroxide, The following conditions (I) and (II): A6 ... (I) 4B / A10 ... (II) (In the formula, A is the polystyrene sulfonate solution after neutralization.
pH, and B indicates the time (minutes) required for neutralization. ) Is satisfied, the polystyrene sulfonic acid remaining in the neutralization solution is then neutralized with an alkali metal hydroxide, and then the alkaline earth metal sulfate in the aqueous solution is separated. A method for producing a polystyrene alkaline earth metal salt is provided.
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５〜10wt％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. Here, as the diluent gas SO 3 , one having a SO 3 concentration of 1 to 12% by volume, preferably 3 to 4% by volume is used, and the diluted liquid SO 3 has an SO 3 concentration of 1 to 50 wt.
%, Preferably 5 to 10 wt%.
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、上記スルホン化により得られた反応生成物
より遠心濾過法及び／又は蒸発法又は水抽出分離法等に
より反応有機溶媒を分離して、ポリスチレンスルホン酸
又はその水溶液を得た後、上記式（Ｉ）及び（II）を満
す条件で中和を行う。尚、ここで遠心濾過法としてはバ
スケットを有する遠心分離機により行うのがよく、蒸発
法としては、減圧フラッシュ蒸発によるのがよく、又、
水抽出としては、特定量の水を加えて、水と有機溶媒と
を層分離し、水層のみを取り出す方法によるのがよい。In the present invention, the reaction organic solvent is separated from the reaction product obtained by the sulfonation by a centrifugal filtration method and / or an evaporation method or a water extraction separation method to obtain polystyrenesulfonic acid or an aqueous solution thereof, Neutralization is carried out under conditions satisfying the formulas (I) and (II). Here, the centrifugal filtration method is preferably performed by a centrifuge having a basket, and the evaporation method is preferably reduced pressure flash evaporation.
The water extraction may be performed by adding a specific amount of water, separating the water and the organic solvent into layers, and taking out only the water layer.
本発明においては、アルカリ土類金属水酸化物を用いた
第１次中和を式（Ｉ）及び（II）の条件に従って行うの
を特徴とし、特に式（Ｉ）中、Ａとしては1.5〜４が好
ましく、又式（II）中、B/Aが５〜６となるように行う
のがよい。ここで、中和に際しては、水酸化カルシウム
や水酸化マグネシウムなどのアルカリ土類金属水酸化物
を５〜50重量％（以下％と略称する。）、好ましくは20
〜40％含み、かつ粒径を100〜500μとした水性分散液を
用いるのが好ましく、又中和されるポリスチレンスルホ
ン酸としては、該スルホン酸を５〜40％、好ましくは10
〜20％含む水溶液を用いるのがよい。特にポリスチレン
スルホン酸を中和するに必要な当量の90〜99.5当量％の
水性分散液を用いるのが望ましい。操作として具体的に
は、該ポリスチレンスルホン酸水溶性のpHを測定しつ
つ、該水溶液のpHが６を越えない程度に、式（II）に従
って、アルカリ土類金属水酸化物水性分散液を添加して
中和を行う。この際、中和反応が一層迅速に行われるよ
うに、0.01N/cm2以上の剪断力を有する撹拌機を備えた
容器中にて、温度20〜80℃、好ましくは30〜50℃で行う
のがよい。The present invention is characterized in that the primary neutralization using an alkaline earth metal hydroxide is carried out according to the conditions of the formulas (I) and (II), and particularly, in the formula (I), A as 1.5 to 4 is preferable, and B / A is 5 to 6 in the formula (II). Here, upon neutralization, an alkaline earth metal hydroxide such as calcium hydroxide or magnesium hydroxide is contained in an amount of 5 to 50% by weight (hereinafter abbreviated as%), preferably 20.
It is preferable to use an aqueous dispersion containing -40% by weight and having a particle size of 100-500μ, and as polystyrene sulfonic acid to be neutralized, the sulfonic acid is 5-40%, preferably 10%.
It is recommended to use an aqueous solution containing ~ 20%. In particular, it is desirable to use an aqueous dispersion of 90 to 99.5 equivalent% of the equivalent required to neutralize polystyrene sulfonic acid. Specifically, as an operation, while measuring the pH of the polystyrene sulfonic acid water-soluble, add an alkaline earth metal hydroxide aqueous dispersion according to the formula (II) so that the pH of the aqueous solution does not exceed 6. And neutralize. At this time, in order to carry out the neutralization reaction more quickly, in a container equipped with a stirrer having a shearing force of 0.01 N / cm 2 or more, the temperature is 20 to 80 ° C., preferably 30 to 50 ° C. Is good.
本発明では、上記中和に次いで、第２次の中和を行う。
すなわち、中和溶液中に残存している未中和のポリスチ
レンスルホン酸や未反応SO3を水酸化ナトリウムや水酸
化カリウムなどのアルカリ金属水酸化物で中和するので
ある。具体的には、１〜10％のアルカリ金属水酸化物の
水溶液を前記中和溶液に添加し、第一次中和と同じ撹拌
条件下、同じ温度で１〜30分行うのがよい。In the present invention, secondary neutralization is performed after the above neutralization.
That is, the unneutralized polystyrene sulfonic acid and unreacted SO 3 remaining in the neutralization solution are neutralized with an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Specifically, it is preferable to add an aqueous solution of an alkali metal hydroxide of 1 to 10% to the neutralization solution and perform the stirring under the same stirring conditions as the primary neutralization at the same temperature for 1 to 30 minutes.
第２次中和後、液中の石こう等のアルカリ土類金属硫酸
塩等を常法により、例えば濾過等により除去してポリス
チレンスルホン酸アルカリ土類金属塩を得る。After the second neutralization, the alkaline earth metal sulfate such as gypsum in the liquid is removed by a conventional method, for example, by filtration to obtain an alkaline earth metal polystyrenesulfonate.
本発明によれば、短時間の中和時間で、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のカルシウム塩
やマグネシウム塩等のアルカリ土類金属塩を容易に高収
率で製造することができる。According to the present invention, it is possible to easily produce a high-purity alkaline earth metal salt such as a calcium salt or a magnesium salt of polystyrene sulfonate having a high degree of purity with less by-products, in a short neutralization time. .
従って、本発明の方法により得られたポリスチレンスル
ホン酸塩は、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できる。次に実施例により本
発明を製造するが、本発明はこれらに限定されるもので
はない。Therefore, the polystyrene sulfonate obtained by the method of the present invention can be widely used as an antistatic agent for paper, a concrete water reducing agent, a dispersant and the like. Next, the present invention will be produced by way of examples, but the present invention is not limited thereto.
実施例 平均分子量4,500又は10,000のポリスチレン50gを1,2ジ
クロルエタン500gに溶解した後、液状SO3（商品名サル
ファン）をスルホン化剤としてSO3モル比1,1の量で用
い、撹拌機付きのスルホン化反応器中、反応温度30℃で
スルホン化を行った。Example After dissolving 50 g of polystyrene having an average molecular weight of 4,500 or 10,000 in 500 g of 1,2 dichloroethane, liquid SO 3 (trade name: sulfane) was used as a sulfonating agent at an SO 3 molar ratio of 1,1 and a stirrer was used. The sulfonation was carried out at a reaction temperature of 30 ° C. in the sulfonation reactor.
スルホン化終了後、ポリスチレンスルホン酸を含む反応
生成物に所定量の水を加えて30℃で撹拌し、静置分離し
て、上層の水層としてポリスチレンスルホン酸不溶液を
得た。これに40％Ca（OH）２水分散液（平均粒径 250
μ）を撹拌下表−１に示す条件で加えて第１次中和を行
い、次いで５％NaOH水溶液を加えて第２次中和を行った
後、濾過して硫酸カルシウムを除去した。条件及び結果
をまとめて表−１に示す。After the completion of the sulfonation, a predetermined amount of water was added to the reaction product containing polystyrene sulfonic acid, the mixture was stirred at 30 ° C., and allowed to stand and separate to obtain a polystyrene sulfonic acid non-solution as an upper aqueous layer. 40% Ca (OH) 2 aqueous dispersion (average particle size 250
μ) was added under stirring under the conditions shown in Table 1 to perform primary neutralization, and then 5% NaOH aqueous solution was added to perform secondary neutralization, followed by filtration to remove calcium sulfate. The conditions and results are summarized in Table-1.
Claims (1)
をハロゲン化炭化水素溶媒中でスルホン化し該溶媒を分
離したポリスチレンスルホン酸を、アルカリ土類金属水
酸化物を含む水性分散液を用いて、次の条件（Ｉ）及び
（II）： Ａ６ ……（Ｉ） ４B/A10 ……（II） （式中、Ａは中和後のポリスチレンスルホン酸塩溶液の
pHであり、Ｂは中和に要する時間（分）を示す。） を満す条件で中和し、次いで中和溶液中に残存するポリ
スチレンスルホン酸をアルカリ金属水酸化物で中和した
後、該水溶液中のアルカリ土類金属硫酸塩を分離するこ
とを特徴とするポリスチレンアルカリ土類金属塩の製造
方法。1. A polystyrene sulfonic acid obtained by sulfonating polystyrene having an average molecular weight of 200 to 50,000 in a halogenated hydrocarbon solvent and separating the solvent, by using an aqueous dispersion containing an alkaline earth metal hydroxide. Conditions (I) and (II): A6 ... (I) 4B / A10 ... (II) (In the formula, A is the polystyrene sulfonate solution after neutralization.
pH, and B indicates the time (minutes) required for neutralization. ) Is satisfied, and then polystyrene sulfonic acid remaining in the neutralization solution is neutralized with an alkali metal hydroxide, and then the alkaline earth metal sulfate in the aqueous solution is separated. A method for producing an alkaline earth metal salt of polystyrene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1996187A JPH0742335B2 (en) | 1987-01-30 | 1987-01-30 | Method for producing alkaline earth metal salt of polystyrene sulfonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1996187A JPH0742335B2 (en) | 1987-01-30 | 1987-01-30 | Method for producing alkaline earth metal salt of polystyrene sulfonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63189405A JPS63189405A (en) | 1988-08-05 |
| JPH0742335B2 true JPH0742335B2 (en) | 1995-05-10 |
Family
ID=12013792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1996187A Expired - Lifetime JPH0742335B2 (en) | 1987-01-30 | 1987-01-30 | Method for producing alkaline earth metal salt of polystyrene sulfonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0742335B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199060A (en) * | 2015-10-14 | 2015-12-30 | 广东红墙新材料股份有限公司 | Super-early-strength PCE (polycarboxylate ether) superplasticizer and preparation method thereof |
| KR20220081105A (en) * | 2020-12-08 | 2022-06-15 | 동아대학교 산학협력단 | Salts of polystyrene sulfonic acid, manufacturing method thereof and compositions |
-
1987
- 1987-01-30 JP JP1996187A patent/JPH0742335B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199060A (en) * | 2015-10-14 | 2015-12-30 | 广东红墙新材料股份有限公司 | Super-early-strength PCE (polycarboxylate ether) superplasticizer and preparation method thereof |
| KR20220081105A (en) * | 2020-12-08 | 2022-06-15 | 동아대학교 산학협력단 | Salts of polystyrene sulfonic acid, manufacturing method thereof and compositions |
| WO2022124522A1 (en) * | 2020-12-08 | 2022-06-16 | 동아대학교 산학협력단 | Polystyrene sulfonate metal salt, production method thereof, and composition including same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63189405A (en) | 1988-08-05 |
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