JPS6169816A - Production of porous copolymer - Google Patents
Production of porous copolymerInfo
- Publication number
- JPS6169816A JPS6169816A JP19193784A JP19193784A JPS6169816A JP S6169816 A JPS6169816 A JP S6169816A JP 19193784 A JP19193784 A JP 19193784A JP 19193784 A JP19193784 A JP 19193784A JP S6169816 A JPS6169816 A JP S6169816A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization initiator
- copolymer
- forming agent
- water
- porosity
- 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
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- Polymerisation Methods In General (AREA)
- 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、多孔質共重合体の製造方法に関するものであ
り、詳しくは、比表面積および細孔容積が高度に発達し
た多孔式共重合体の製造方法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a porous copolymer, and more specifically, a porous copolymer having a highly developed specific surface area and pore volume. The present invention relates to a manufacturing method.
従来、非極性もしくは微極性の球状架橋共重合体のうち
で比表面積および細孔容積を充分く発達させたものは、
合成吸着剤と呼ばれ、その細孔表面への物理吸着を利用
して水中に存する有機物の吸着剤として多用されている
。Conventionally, among nonpolar or slightly polar spherical crosslinked copolymers, those with sufficiently developed specific surface area and pore volume are
It is called a synthetic adsorbent and is widely used as an adsorbent for organic substances present in water by utilizing its physical adsorption on the pore surface.
かかる合成吸着剤の製造方法は公知であり、例えば、モ
ノビニル化合物、ポリビニル化合物および多孔質化剤の
混合物を水中で懸濁重合した後、得られた架橋共重合体
より多孔質化剤を除去する方法があり、多孔質化剤とし
ては、有機溶媒、可塑剤または線状ポリマーあるいはこ
れらの混合物が用いられる。しかしながら、このような
従来法でイひられた架橋共重合体の比表面積、細孔容積
は必ずしも充分ではなく、その改善が望まれている。Methods for producing such synthetic adsorbents are known, and include, for example, suspension polymerization of a mixture of a monovinyl compound, a polyvinyl compound, and a porosity-enhancing agent in water, and then removing the porosity-enhancing agent from the resulting crosslinked copolymer. The porosity forming agent is an organic solvent, a plasticizer or a linear polymer or a mixture thereof. However, the specific surface area and pore volume of the crosslinked copolymers produced by such conventional methods are not necessarily sufficient, and improvement thereof is desired.
本発明の目的は、前記従来法を改善して一層高められた
比表面積および細孔容積を有する多孔質共重合体の製造
方法を提供することにある。An object of the present invention is to provide a method for producing a porous copolymer having an even higher specific surface area and pore volume by improving the conventional method.
しかして、本発明の目的は、モノビニル化合物、ポリビ
ニル化合物および多孔質化剤の混合物を全単量体に対し
て３〜ｌコ重ｆｉ％の重合開始剤の存在下、水中で懸濁
重合して多孔質共重合体を得、次いで、核多孔質共重合
体を加熱処理後多孔質化剤を除去することによシ容易に
達成される。Therefore, the object of the present invention is to carry out suspension polymerization of a mixture of a monovinyl compound, a polyvinyl compound, and a porosity-forming agent in water in the presence of a polymerization initiator of 3 to 1 copolymerization fi% based on the total monomers. This can be easily achieved by obtaining a porous copolymer by heating the core porous copolymer, and then removing the porosity-enhancing agent after heat-treating the core porous copolymer.
該球状架橋共重合体を構成するモノビニル化合物として
はスチレン、ビニルトルエン、ビニルナフタリン、エチ
ルビニルベンゼン、等の芳香族モノビニル単量体、ビニ
ルピリジン、等のモノビニル複素環化合物、メタクリル
酸、アクリル、酸およびそれらのエステル頌、アクリロ
ニトリル、メタクリレートリル等のモノビニル化合物が
有用である。The monovinyl compounds constituting the spherical crosslinked copolymer include aromatic monovinyl monomers such as styrene, vinyltoluene, vinylnaphthalene, and ethylvinylbenzene, monovinyl heterocyclic compounds such as vinylpyridine, methacrylic acid, acrylic acid, and acid. and their esters, and monovinyl compounds such as acrylonitrile and methacrylatetrile are useful.
ポリビニル化合物としてはジビニルベンゼン、トリビニ
ルベンゼン、ジビニルトルエン、ジビニルキシレン、等
のポリビニル芳香族化合物、ジビニルピリジン等のポリ
ビニル複素環化合物、エチレングリコールジメタクリレ
ート、トリメチロールプロパントリメタクリレート等の
ポリビニルエステル化合物の如きラジカル重合活性な二
重結合を二つ以上有する化合物が有用である。Examples of polyvinyl compounds include polyvinyl aromatic compounds such as divinylbenzene, trivinylbenzene, divinyltoluene, and divinylxylene, polyvinyl heterocyclic compounds such as divinylpyridine, and polyvinyl ester compounds such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate. Compounds having two or more radical polymerization-active double bonds are useful.
これらのモノビニル化合物の混合比率は任意の割合で変
え得るが、架橋剤であるポリビニル化合物の全ビニル化
合物に対する割合はｒ〜１０重量％好ましくは７５〜１
０重量−の範囲で選定される。The mixing ratio of these monovinyl compounds can be changed at any ratio, but the ratio of the polyvinyl compound as a crosslinking agent to the total vinyl compounds is r~10% by weight, preferably 75~1
It is selected in the range of 0 weight -.
ポリビニル化合物の量が！重量％より低いと架橋共重合
体の多孔質化度が低く本発明の効果を発現しにくい。The amount of polyvinyl compounds! If it is lower than % by weight, the degree of porosity of the crosslinked copolymer will be low, making it difficult to exhibit the effects of the present invention.
多孔質化剤としては、有機溶媒、可Φ剤および線状ポリ
マーが使用され、具体的には、トルエン、ベンゼン等の
芳香族化合物、酢酸エチル、酢酸ブチル等のエステル系
化合物、イソアミルアルコール、メチルイソブチルカル
ビノール等のアルコール０％ ｎ−へブタン、イノオク
タン等のべ１和炭化水素類、ジクロルエタン、トリクＯ
Ａ、 ！ ｆ Ｌ／ン等のハロゲン系溶媒、７タル酸ジ
オクチル、アジピン酸ジブチル等の可塑剤、ポリスチレ
ン、ポリ酢酸ビニル等のポリマー等が有用である。Organic solvents, Φ softeners, and linear polymers are used as porosity agents, and specifically, aromatic compounds such as toluene and benzene, ester compounds such as ethyl acetate and butyl acetate, isoamyl alcohol, and methyl 0% alcohol such as isobutyl carbinol, monomerized hydrocarbons such as n-hebutane and inooctane, dichloroethane, tric-O
A,! Halogenated solvents such as f L/N, plasticizers such as dioctyl heptalate and dibutyl adipate, and polymers such as polystyrene and polyvinyl acetate are useful.
多孔質化剤の使用割合は、有機溶媒および可塑剤を使用
する場合には、全単量体に対しｊ。When using an organic solvent and a plasticizer, the proportion of the porosity-forming agent to be used is j based on the total monomer.
〜−！Ｏ重ｔ％、線状ポリマーを用いる場合には全単量
体に対しｌ−２ＯＮ量チ用いる。~-! When a linear polymer is used, an amount of 1-2ON is used based on the total monomer.
モノビニル化合物、ポリビニル化合物および多孔質化剤
の混合物は公知の方法に従って懸濁重合される。その際
、重合開始剤としては過酸化ベンゾイル、過酸化ラウロ
イル、ｔ−ブチルハイドロパーオキサイト、アゾビスイ
ンブチロニトリル等が用いられ、通常全モノマーに対し
て０．／〜１重量重量％用いられる。しかしながら本発
明に於いては３〜／コ重ｆチ、好ましくは５〜ｉｏ重量
％用いる。３重量−未満でちると本発明の目的を達成す
ることが難かしくなり、１２重ｔチ超であると、ラジカ
ル分解の発熱が多くなって重合コントロールが難かしく
なると共に、分子量が小さくなるので好ましくない。The mixture of monovinyl compound, polyvinyl compound and porosity-forming agent is suspension polymerized according to known methods. At that time, as a polymerization initiator, benzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, azobisin butyronitrile, etc. are used, and usually 0. /~1% by weight is used. However, in the present invention, it is used in an amount of 3 to 10% by weight, preferably 5 to 10% by weight. If the weight is less than 3 weight, it will be difficult to achieve the object of the present invention, and if it exceeds 12 weight, the heat generated by radical decomposition will increase, making it difficult to control polymerization, and the molecular weight will become small. Undesirable.
このｌ！Ｉ！！濁重合は通常単量体混合物／容積に対し
、／〜ｊ容積の水を加え、懸濁安定剤存在下に加温する
ことによシ行なわれる。懸濁安定剤としてはゼラチン、
メチルセルロース、ポリアクリル酸ノーダボリビニルア
ルコール等公知のも、のが使用出来る。重合は使用する
重合開始剤の種類により、その温度および時間が異なる
が本発明では重合終了時に用いた重合開始剤の１０〜Ｐ
０重λ饅、好ましくは３０〜１０重ｆ；にチが残存する
様な条件で重合を行なうことが望ましい。This l! I! ! Suspension polymerization is usually carried out by adding /~j volumes of water to the monomer mixture/volume and heating in the presence of a suspension stabilizer. Gelatin as a suspension stabilizer;
Known materials such as methyl cellulose and polyacrylic acid non-vinyl alcohol can be used. The temperature and time of polymerization differ depending on the type of polymerization initiator used, but in the present invention, the polymerization initiator used at the end of polymerization is
It is desirable to carry out the polymerization under conditions such that 0% λ, preferably 30 to 10%, remains.
重合終了後、重合体は水洗され、次いで、重合体中に残
存する多孔質化剤は、公知の方法に従って除去されるが
、この方法では重合体中の多孔質化剤が減少するにつれ
、重合体が収縮し、かつ重合体中にその時点で残存する
ポリビニル化合物の側鎖の二重結合が熱架橋することに
より重合体の不可逆的な収縮を生じ、ひいては細孔物性
な低下を生ずる。After the polymerization is completed, the polymer is washed with water, and then the porosity-forming agent remaining in the polymer is removed according to a known method. In this method, as the porosity-forming agent in the polymer decreases, The coalescence shrinks, and the double bonds in the side chains of the polyvinyl compound remaining in the polymer at that point are thermally crosslinked, resulting in irreversible shrinkage of the polymer and, as a result, a decrease in pore physical properties.
本発明に於いては、この様な細孔物性の低下を防ぐ為に
、架橋共重合体を多孔質化剤の除去に先立ち、加熱する
ことを特徴とする。この加熱処理の目的は、重合体中に
含有する多孔質化剤有機溶媒が系外圧除去されることな
く、残存する重合開始剤の加熱分解により、残存二重結
合を消滅させることにある。かかる目的の為に％本発明
に於いては前述の如く、従来法と異なって多量の重合体
の加熱は、該共重合体を重合系から分離して単独で行う
こともできるが、多孔質化剤が極力逸散しない条件下で
行うのが好ましく、具体的には、有機溶媒または水の中
で行うのが好ましい。特には、水中で行うのが好適であ
る。In order to prevent such deterioration of pore physical properties, the present invention is characterized in that the crosslinked copolymer is heated prior to removing the porosity-forming agent. The purpose of this heat treatment is to eliminate residual double bonds by thermally decomposing the remaining polymerization initiator without removing the external pressure of the porosity-forming agent organic solvent contained in the polymer. For this purpose, in the present invention, as mentioned above, unlike the conventional method, heating a large amount of polymer can be performed by separating the copolymer from the polymerization system and heating it alone; It is preferable to carry out the reaction under conditions that prevent the oxidizing agent from escaping as much as possible, and specifically, it is preferable to carry out the reaction in an organic solvent or water. In particular, it is preferable to carry out the process underwater.
加熱は、加熱終了時に残存する重合開始剤が、用いた重
合開始剤の／チ以下になる様な条件で行９ことが好まし
く、一般的には９０〜／コＯ℃でλ〜ｒ時間加熱するこ
とがすすめられる。Heating is preferably carried out under conditions such that the amount of polymerization initiator remaining at the end of heating is less than 10% of the polymerization initiator used, and is generally heated at 90 to 10°C for λ to r hours. It is recommended that you do so.
加熱処理を行った架橋共重合体は、多孔質化剤が除去さ
ｔＬるが、除去は公知の方法に従って行うことができ、
例えば、多孔質化剤として有機溶媒を用いた場合は、溶
剤洗浄、共沸蒸留等によって行うことができ、可塑剤や
線状ポリスチレンを用いた場合は、溶剤抽出によって行
９ことができる。多孔質化剤が除かれた架橋共重体は水
洗し、必要に応じてアルコール等の有機溶媒で洗浄した
後、使用に供される。The porosity-forming agent is removed from the heat-treated crosslinked copolymer, but removal can be performed according to a known method,
For example, when an organic solvent is used as the porosity-forming agent, it can be carried out by solvent washing, azeotropic distillation, etc., and when a plasticizer or linear polystyrene is used, it can be carried out by solvent extraction. The crosslinked copolymer from which the porosity-forming agent has been removed is washed with water and, if necessary, with an organic solvent such as alcohol, before being used.
以下、実施例により本発明を更に詳細に説明するが、本
発明は以下の実施例に限定されるものではない。EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples.
実施列−／
Ｍｌｌｉ７％のジビニルベンゼンタフ２、スチレン３２
％ トルエンｔ ｓ ｏ ｆ、 過酸化ベンゾイル７２
よりなる単量体混合物をポリビニルアルコール／、コｉ
ｔを含む７タＯｗｌ中に懸濁し、１０℃−ｒ時間、窒素
下に加熱攪拌することにより直径ｏ、ｒ〜／、ＯＴｒｒ
ｍの粒径を有する共重合体を得た。この重合体を水洗Ｐ
別し、水６００ｍ１中に加え、１００℃にて６時間加熱
処理した。Practical row - / Mlli 7% divinylbenzene tough 2, styrene 32
% toluene tsof, benzoyl peroxide 72
A monomer mixture consisting of polyvinyl alcohol/coi
diameter o, r~/, OTrr by suspending it in 7 Owl containing t and heating and stirring under nitrogen for 10°C-r hours.
A copolymer having a particle size of m was obtained. Wash this polymer with water
The mixture was separated, added to 600 ml of water, and heated at 100° C. for 6 hours.
次いで、該架橋共重合体をＰ別し、水ＡＯＯｙｔｌ中に
加え、ｒり℃にて下気圧下に加熱することにより、残存
トルエンを留去した。得られた共重合体を次いで乾燥し
、収量、細孔物性を測定した。結果を表−／に記した。Next, the crosslinked copolymer was separated from P, added to water (AOOytl), and heated under a lower pressure at 0.degree. C. to distill off residual toluene. The obtained copolymer was then dried, and the yield and pore physical properties were measured. The results are shown in Table-/.
比較例−／（水中で加熱処理のない例）実施例−／に於
いて、水中で加熱処理をしない以外は、実施例−７と全
く同様に処理し、共重合体を得た。結果を表−ｌに記し
た。Comparative Example-/(Example without heat treatment in water) In Example-/, a copolymer was obtained by carrying out the treatment in exactly the same manner as in Example-7 except that the heat treatment in water was not performed. The results are shown in Table 1.
実施例−１
実施例−１に於いて、スチレン３２の代りにメタクリル
酸メチル３′？、過酸化ベンゾイル７２の代りに、アゾ
ビスイソブチロニトリル７１を使した以外は、実施例−
７と全く同様に処理して架橋共重合体を得た。結果を表
−２に記した。Example-1 In Example-1, styrene 32 was replaced with methyl methacrylate 3'? , Example - except that azobisisobutyronitrile 71 was used instead of benzoyl peroxide 72.
A crosslinked copolymer was obtained by treatment in exactly the same manner as in 7. The results are shown in Table-2.
比較例−λ
実施例−２に於ける水中での加熱処理をしない以外は実
施例−２と全く同様に処理し、共重合体を得九。結果を
表−２に記した。Comparative Example -λ A copolymer was obtained in the same manner as in Example 2 except that the heat treatment in water was not carried out. The results are shown in Table-2.
比較例−３
実施例−７に於いて、過酸化ベンゾイル７１の代りに、
Ａｖ化ベンゾイル／ｌを使用した以外は、実施列−ｌと
全く同様に処理し、共重合体を得た。結果を表−ｌに記
した。Comparative Example-3 In Example-7, instead of benzoyl peroxide 71,
A copolymer was obtained by processing in exactly the same manner as in Example 1, except that benzoyl Av/l was used. The results are shown in Table 1.
表−／
表−２
〔発明の効果〕
本発明によれば、比表面積、細孔容遺共高い多孔質共重
合体が得られる。Table/Table 2 [Effects of the Invention] According to the present invention, a porous copolymer with high specific surface area and high pore volume can be obtained.
Claims (3)
質化剤の混合物を重合開始剤の存在下、水中で懸濁重合
して架橋共重合体を得、該架橋共重合体より多孔質化剤
を除去する多孔質共重合体の製造方法であつて、懸濁重
合を全単量体に対して３〜１２重量％の重合開始剤の存
在下に行い且つ架橋共重合体を多孔質化剤の除去に先立
ち、加熱処理することを特徴とする多孔質共重合体の製
造方法。(1) A mixture of a monovinyl compound, a polyvinyl compound, and a porosity-enhancing agent is subjected to suspension polymerization in water in the presence of a polymerization initiator to obtain a crosslinked copolymer, and the porosity-enhancing agent is removed from the crosslinked copolymer. A method for producing a porous copolymer, comprising carrying out suspension polymerization in the presence of a polymerization initiator in an amount of 3 to 12% by weight based on the total monomers, and removing the porosity-forming agent from the crosslinked copolymer. A method for producing a porous copolymer, which comprises first performing a heat treatment.
請求の範囲第１項記載の多孔質共重合体の製造方法。(2) The method for producing a porous copolymer according to claim 1, wherein the heat treatment is performed in water.
終了時に残存条件下で行われることを特徴とする特許請
求の範囲第１項又は第２項記載の多孔質共重合体の製造
方法。(3) The porous copolymer according to claim 1 or 2, wherein the suspension polymerization is carried out under conditions in which 10 to 90% by weight of the polymerization initiator remains at the end of the polymerization. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59191937A JPH0621124B2 (en) | 1984-09-13 | 1984-09-13 | Method for producing porous copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59191937A JPH0621124B2 (en) | 1984-09-13 | 1984-09-13 | Method for producing porous copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6169816A true JPS6169816A (en) | 1986-04-10 |
| JPH0621124B2 JPH0621124B2 (en) | 1994-03-23 |
Family
ID=16282932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59191937A Expired - Fee Related JPH0621124B2 (en) | 1984-09-13 | 1984-09-13 | Method for producing porous copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0621124B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2783678A1 (en) | 2013-03-28 | 2014-10-01 | Sekisui Plastics Co., Ltd. | Porous resin particles, method of manufacturing the same, and use of the same |
| US9200154B2 (en) | 2012-03-27 | 2015-12-01 | Sekisui Plastics Co., Ltd. | Porous resin particles, method of manufacturing the same, and use of the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51144394A (en) * | 1975-06-09 | 1976-12-11 | Asahi Chem Ind Co Ltd | Process for producing porous anion exchange resin |
| JPS51144393A (en) * | 1975-06-09 | 1976-12-11 | Asahi Chem Ind Co Ltd | Process for producing porous anion exchange resin |
| JPS5759847A (en) * | 1980-09-29 | 1982-04-10 | Hisamitsu Pharmaceut Co Inc | 4-aminomethylcyclohexanecarboxylic acid derivative |
| JPS5817526A (en) * | 1981-07-24 | 1983-02-01 | Canon Electronics Inc | Coil bobbin |
-
1984
- 1984-09-13 JP JP59191937A patent/JPH0621124B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51144394A (en) * | 1975-06-09 | 1976-12-11 | Asahi Chem Ind Co Ltd | Process for producing porous anion exchange resin |
| JPS51144393A (en) * | 1975-06-09 | 1976-12-11 | Asahi Chem Ind Co Ltd | Process for producing porous anion exchange resin |
| JPS5759847A (en) * | 1980-09-29 | 1982-04-10 | Hisamitsu Pharmaceut Co Inc | 4-aminomethylcyclohexanecarboxylic acid derivative |
| JPS5817526A (en) * | 1981-07-24 | 1983-02-01 | Canon Electronics Inc | Coil bobbin |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9200154B2 (en) | 2012-03-27 | 2015-12-01 | Sekisui Plastics Co., Ltd. | Porous resin particles, method of manufacturing the same, and use of the same |
| EP2783678A1 (en) | 2013-03-28 | 2014-10-01 | Sekisui Plastics Co., Ltd. | Porous resin particles, method of manufacturing the same, and use of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0621124B2 (en) | 1994-03-23 |
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