JPS58149905A - Sulfonation of polyolefin - Google Patents
Sulfonation of polyolefinInfo
- Publication number
- JPS58149905A JPS58149905A JP3242882A JP3242882A JPS58149905A JP S58149905 A JPS58149905 A JP S58149905A JP 3242882 A JP3242882 A JP 3242882A JP 3242882 A JP3242882 A JP 3242882A JP S58149905 A JPS58149905 A JP S58149905A
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin
- fuming sulfuric
- surfactant
- sulfuric acid
- surface area
- 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
Abstract
Description
【発明の詳細な説明】
本発明は、ポジオレフィン粉末あるいは締維などの比表
面積の大きいポリオレフィンのスルホン化方法に関する
ものである、
ポリオレフィンを発煙硫酸中でスルホン化する方法は知
られているが、ポリオレフィン粉末あるいは線維などの
重量に比し表面積の大きい、すなわち比表面積の大きい
形状のものについては、均質なスルホン化−を得ること
は困難である。その理由は、−ポリオレアインが疎水性
であシ、水濡れ性が悪いため、比表面積が大きい形状の
奄のでは、全面にわたって発煙硫酸で均一に処理されな
いからであるＣ％に微粉末のポリオレフィンは、一般に
二次凝集しているため、粒子間にまで全面にわたって発
煙硫酸が浸漬され難い。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for sulfonating polyolefins having a large specific surface area, such as podioolefin powder or fibers. Although a method for sulfonating polyolefins in oleum is known, It is difficult to obtain homogeneous sulfonation for polyolefin powders or fibers that have a large surface area relative to their weight, that is, have a large specific surface area. The reason for this is that polyolefin is hydrophobic and has poor water wettability, so if the polyolefin has a large specific surface area, it cannot be treated uniformly over the entire surface with fuming sulfuric acid. Since the particles are generally secondary agglomerated, it is difficult for the fuming sulfuric acid to be immersed over the entire surface even between the particles.
本発明者は、上記従来法における一点を解消するため研
究を進めた結果、ポリオレフィンｔ−発煙硫酸中で反応
させる前・に、あらかじめ表面活性剤で処理しておくと
、きわめて均質なスルホン化物が得られることを知り、
本発明を完成するに到ったのである。すなわち、本発明
は、比＃ｃＩｆｌ積が１００ｃ１１／ｆ以上のポリオ、
しフィンを発煙硫酸中でスルホン化するに当り、あらか
じめ表面活性剤で処理し九ポリオレフィンを、Ｓ０３
として１〜２０−を含有する発煙硫酸中に分散させて反
応させることを％黴とするポリオレフィンのスルホン化
方法である、
本発明においてポリオレフィンとは、ポリエチーレン、
ポリプロピレン、ポリブテン、まえはエチレン、１０ピ
レン、ブテン、ヘキセン、塩化ビ二ル等オレフィンの２
種以上の共重合体、またはこれらの２１ｍ以上のポリマ
ーよシなる製品、あるいはこれらの混合物である。As a result of conducting research to solve one problem in the above-mentioned conventional method, the present inventor found that by treating polyolefin t with a surfactant in advance before reacting it in oleum, an extremely homogeneous sulfonated product can be obtained. Knowing what you can get,
The present invention has now been completed. That is, the present invention provides polio with a ratio #cIfl product of 100c11/f or more,
Before sulfonating the polyolefin in fuming sulfuric acid, the 9-polyolefin was treated with a surfactant in advance and
This is a method for sulfonating polyolefins by dispersing and reacting them in fuming sulfuric acid containing 1 to 20-. In the present invention, polyolefins refer to polyethylene,
Polypropylene, polybutene, ethylene, pyrene, butene, hexene, vinyl chloride, and other olefins
It is a copolymer of more than one species, a product made of a polymer of 21 m or more, or a mixture thereof.
本発明は、ポリオレフィン粉末あるいは繊維のように比
表面積の大きいもの、ｉ般に、比表面積が１００７／ｆ
以上のものに有効であシ、竹に３００ｄｌ？以上で、粒
子、繊維等が二次凝集ま九は会合している場合、表面が
顕微鏡観察で複雑な形状をしている場合には、本発明の
方法において始めて、均質で親木性を有する製品とする
ことができる。The present invention is applicable to materials having a large specific surface area such as polyolefin powder or fibers, and generally having a specific surface area of 1007/f.
Is it effective for the above, 300 dl for bamboo? As described above, if the particles, fibers, etc. are aggregated or aggregated together, or if the surface has a complicated shape when observed under a microscope, the method of the present invention can be used to obtain homogeneous and parent-like properties. It can be a product.
本発明の表面活性剤としては、低濃度で著しい表面活性
を有するもので、親水基と親油基とな持ち、強酸中で安
定なものであれば使用できる。例えば、高級アミンハロ
ゲン酸塩、第４アンモニウム塩、ハロゲン化アルキルピ
リジニウム等のカチオン型表面活性剤、ポリエチレング
リコールアルキルエーテル等のノニオン型表面活性剤が
ある。As the surfactant of the present invention, one can be used as long as it has remarkable surface activity at low concentration, has both hydrophilic and lipophilic groups, and is stable in strong acids. Examples include cationic surfactants such as higher amine halogenates, quaternary ammonium salts, and alkylpyridinium halides, and nonionic surfactants such as polyethylene glycol alkyl ether.
本発明においては、後記実施例から明らかなように、特
に７ニオン製表ＩＯ活性剤が好ましく、ＨＬＢ（親水性
親油性バランス）１０〜１８のものがよ上記表面活性剤
によるポリオレフィンの処理は、表面活性剤のアルコー
ル溶液をポリオレフィンに含浸させ丸後、アルコールを
乾燥除去することによって行われる。In the present invention, as is clear from the examples below, 7-ion surface IO surfactants are particularly preferred, and those with an HLB (hydrophilic-oleophilic balance) of 10 to 18 are preferable. This is carried out by impregnating a polyolefin with an alcoholic solution of a surfactant, followed by drying and removing the alcohol.
発煙硫酸中に含まれるＳｏｓの量は１〜２０ｇ＆で化に
長時間を要するため好ましくない。The amount of Sos contained in the fuming sulfuric acid is 1 to 20 g, which is not preferable because it takes a long time to convert.
本発明によってスルホン化され九ポリオレフィンは、カ
ラム等への充填材、焼結体用材料として有用であり、特
にミクロフィルター、印刷ロール、起泡板等の精度が要
求される分野において有効である。スルホン化の均一性
の低いものは、前記のような高い精度を要求される分野
では製品となシえないものであり、本発明の均一にスル
ホン化され九本のにおいて始めて達成することができる
。The sulfonated polyolefin according to the present invention is useful as a filler for columns, etc., and as a material for sintered bodies, and is particularly effective in fields where precision is required, such as microfilters, printing rolls, and foam plates. Products with low uniformity of sulfonation cannot be used as products in fields that require high precision as described above, and this can only be achieved with the uniform sulfonation of the present invention. .
そして、スルホン化されたポリオレアインは、通常、苛
性ソーダ、アンモニア等のアルカリ水溶液で中和して製
品とするが、本発明の製品は、高い親水性を発揮すると
共に、ポリオレフィン自身が疎水性で、耐薬品性が大き
いため、従来の親水性ポリマーのように吸水して膨潤し
たシ、成形品が変形するというようなことがないため、
長時間に亘って安定なＩＩＩＩＩ＠を持続することがで
きる。Sulfonated polyolein is normally made into a product by neutralizing it with an alkaline aqueous solution such as caustic soda or ammonia, but the product of the present invention exhibits high hydrophilicity, and the polyolefin itself is hydrophobic, making it resistant. Because it has high chemical properties, it does not absorb water and swell, unlike conventional hydrophilic polymers, and does not cause molded products to deform.
Stable III@ can be maintained for a long time.
次に、本発明の実施例を挙けて説明する。Next, examples of the present invention will be described.
実施例
表に示す％株の表面活性剤の５嘔メタノ一ル溶ＩＫ％！
！に示すポリオレフィン製品を浸漬した後、溶剤を減圧
乾燥して除去する。発煙硫酸反応液は。5% methanol soluble IK% of the surfactants shown in the Examples table!
! After soaking the polyolefin product shown in , the solvent is removed by drying under reduced pressure. Fuming sulfuric acid reaction solution.
市販の発煙硫酸（８へ ２８％）を稀釈して調整し、８
０、含有量は稀釈度から算出し九。この反応液に前記ポ
リオレフィンを添加して、室温において、ｊ！！に示す
とおりの時間反応させる。その結果は表に示すとおりで
あつ九。Dilute and adjust commercially available fuming sulfuric acid (8 to 28%),
0, the content is calculated from the degree of dilution and is 9. The polyolefin was added to this reaction solution, and j! was added to the reaction solution at room temperature. ! Incubate for the time indicated. The results are as shown in the table.
上記の表において、比表面積は、顕微鏡観察により、粒
子、縁線の必要なサイズを測定し、表面が平滑なものと
して、該製品の密度から算出した。In the above table, the specific surface area was calculated from the density of the product by measuring the required size of particles and edge lines by microscopic observation and assuming that the surface was smooth.
交換当量は次のようにして算出した。スルホン化された
スルホン酸（−８０，）Ｉ） ｍのポリオレフィン製品
（Ｗｆ）を採シ、１規定の塩化カルシウム水溶液中に浸
漬して平衡状態とし、その水溶液中に発生した塩化水素
を０．１規定の苛性ソーダ水溶液（力価ｆ）で滴定し、
フェノールフタレインによる中和値（Ｘα）を求め、下
式によシ算出した。The exchange equivalent was calculated as follows. A polyolefin product (Wf) containing sulfonated sulfonic acid (-80,)I) is sampled and immersed in a 1N aqueous calcium chloride solution to reach an equilibrium state, and the hydrogen chloride generated in the aqueous solution is reduced to 0. Titrated with a 1N aqueous solution of caustic soda (potency f),
The neutralization value (Xα) by phenolphthalein was determined and calculated according to the following formula.
１７１０−、 ｆ ＠ｘ
又換当量■□（ミリ当量／グラム）
なお、イオン交換能を必要としない用途に用いる場合に
は、通常、スルホン酸塩（−ＳへＭ（ＭはＮ＆、 Ｋ、
Ｃａ 、 Ｍｇ、 Ｎ１％等を表わす）〕型とすること
が望ましい。1710-, f @x Exchange equivalent ■□ (milliequivalent/gram) When used for applications that do not require ion exchange ability, it is usually used to convert sulfonate (-S to M (M is N&, K,
It is preferable to use the type (representing Ca, Mg, N1%, etc.).
水濡れ性は粉末成形品、繊維、樹脂片（ペレット）を用
いて行った結果である。粉末成形品は、厚み５ａｍ、直
径１００闘の成形体が得られるようなアルミ製金型に、
約２２ｆの粉末を均一に充填し、それぞれの樹脂の軟化
点近傍の温度で約２０分間加熱して成形しえものである
。この粉末成形品に水を滴下して、吸水速度から判定、
また、線維、樹脂片（ペレット）は、静かに水１ｆＩＩ
ＩＣ浮かべ、接触角、水中への沈み具合いから判定した
。なお、！！においては、下記の水濡れ性の度合を示す
記号で記載した。Water wettability was measured using powder molded products, fibers, and resin pieces (pellets). The powder molded product is placed in an aluminum mold that can produce a molded product with a thickness of 5 am and a diameter of 100 mm.
Approximately 22 f of powder is uniformly filled and molded by heating for approximately 20 minutes at a temperature near the softening point of each resin. Water is dropped onto this powder molded product, and judgment is made from the water absorption rate.
In addition, gently wash the fibers and resin pieces (pellets) with 1fII of water.
Judgment was made from IC floating, contact angle, and degree of sinking into water. In addition,! ! In , the following symbols are used to indicate the degree of water wettability.
◎・・・・・・・・・瞬時に吸収
○・・・・・・・・・１０秒程度で吸収Δ・・・・・・
・・・３０秒程度で吸収Ｘ・・・・・・・・・全く吸収
しない◎・・・・・・Absorbs instantly ○・・・・・・Absorbs in about 10 seconds Δ・・・・・・
...Absorbed in about 30 seconds...... Not absorbed at all
Claims (1)
発煙Ｗ１＃２中でスルホン化するに当シ、あらかじめ！
１面活性剤で処理し九ポリオレフィンを、ＳＯ８として
１〜２０％を含有する発煙硫酸中に分散させて反応させ
ることを４１像とするポリオレフィンのスルホン化方法
。Before sulfonating a polyolefin with a specific surface area of 1 o allf or more in fuming W1#2, be sure to do so in advance!
A method for sulfonating a polyolefin, which comprises dispersing and reacting a polyolefin treated with a surfactant in fuming sulfuric acid containing 1 to 20% as SO8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3242882A JPS58149905A (en) | 1982-03-03 | 1982-03-03 | Sulfonation of polyolefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3242882A JPS58149905A (en) | 1982-03-03 | 1982-03-03 | Sulfonation of polyolefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58149905A true JPS58149905A (en) | 1983-09-06 |
| JPH0363563B2 JPH0363563B2 (en) | 1991-10-01 |
Family
ID=12358678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3242882A Granted JPS58149905A (en) | 1982-03-03 | 1982-03-03 | Sulfonation of polyolefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58149905A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01132044A (en) * | 1987-11-17 | 1989-05-24 | Matsushita Electric Ind Co Ltd | Separator for battery |
| US4965322A (en) * | 1987-04-06 | 1990-10-23 | Asahi Kasei Kogyo Kabushiki Kaisha | Photosensitive and heat-sensitive polymers, process for producing the same and process for recording information using the same |
| WO2007044353A2 (en) * | 2005-10-04 | 2007-04-19 | Ballard Power Systems Inc. | Methods for making sulfonated non-aromatic polymer electrolyte membranes |
-
1982
- 1982-03-03 JP JP3242882A patent/JPS58149905A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4965322A (en) * | 1987-04-06 | 1990-10-23 | Asahi Kasei Kogyo Kabushiki Kaisha | Photosensitive and heat-sensitive polymers, process for producing the same and process for recording information using the same |
| JPH01132044A (en) * | 1987-11-17 | 1989-05-24 | Matsushita Electric Ind Co Ltd | Separator for battery |
| WO2007044353A2 (en) * | 2005-10-04 | 2007-04-19 | Ballard Power Systems Inc. | Methods for making sulfonated non-aromatic polymer electrolyte membranes |
| WO2007044353A3 (en) * | 2005-10-04 | 2007-06-21 | Ballard Power Systems | Methods for making sulfonated non-aromatic polymer electrolyte membranes |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0363563B2 (en) | 1991-10-01 |
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