JP2005120113A - Liquid absorbing agent for organic solvent or organic aqueous solution - Google Patents
Liquid absorbing agent for organic solvent or organic aqueous solution Download PDFInfo
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Abstract
Description
本発明は、アルキル（メタ）アクリルアミドと２官能性以上のモノマーを共重合して成る重合体を含有する事を特徴とする有機溶媒又は有機水溶液吸液剤に関する。 The present invention relates to an organic solvent or an organic aqueous solution absorbent comprising a polymer obtained by copolymerizing an alkyl (meth) acrylamide and a bifunctional or higher functional monomer.
従来、吸収剤としてポリアクリル酸系重合体を筆頭に、澱粉系、ポバール系、セルロース系の重合体が、紙おむつ、生理用品等の衛生材料、及び芳香剤、消臭剤並びに保水剤として汎用的に使用されている。しかしながら、これら重合体の吸収剤は、有機溶媒及び有機水溶液に対する吸液能力が全くなかったり、吸収能力はあっても極めて低いものであった。
そこで、有機水溶液を有効に吸液できるものとして、ポリビニルアセトアミド系重合体が報告されており（特許文献１）、例えば特許文献２には、Ｎ−ビニルアセトアミドとアクリルアミド誘導体からなる共重合体と架橋剤及び可塑剤を含有した吸収材料用組成物が報告されている。
しかしながら、これらポリビニルアセトアミド系重合体を含有した組成物に於いても充分な吸液能力を有しているとは言えず、また、特にアルコール水溶液を効果的に吸液固化できる吸液剤は殆どなく、その開発が望まれていた。
In view of this, a polyvinyl acetamide polymer has been reported as one that can effectively absorb an organic aqueous solution (Patent Document 1). For example, Patent Document 2 discloses a cross-linking with a copolymer of N-vinylacetamide and an acrylamide derivative. A composition for an absorbent material containing an agent and a plasticizer has been reported.
However, it cannot be said that the composition containing these polyvinyl acetamide polymers has sufficient liquid absorbing ability, and there is almost no liquid absorbing agent that can effectively absorb and solidify an aqueous alcohol solution. The development was desired.
本発明の課題は、有機溶媒及び有機水溶液、特にアルコール水溶液、を効果的に吸液できる吸液剤組成物を提供することにある。 An object of the present invention is to provide a liquid absorbent composition capable of effectively absorbing an organic solvent and an organic aqueous solution, particularly an alcohol aqueous solution.
本発明者らは、特定の構造を有するモノマーと架橋剤を共重合させる事により課題を解決できることを見いだし、本発明を完成するに至った。
即ち、本発明は、
（１）一般式（１）（式中、Ｒ１は水素原子又はメチル基を、Ｒ２及びＲ３はＣｎＨ（２ｎ＋１）基（ここでｎは１以上４以下の自然数を表す。）を表す。）で表されるアルキル（メタ）アクリルアミドと、２官能性以上のモノマーを、共重合して成る共重合体を含有する事を特徴とする有機溶媒又は有機水溶液吸液剤、
（２）一般式（１）で表されるアルキル（メタ）アクリルアミドがジメチルアクリルアミドである、上記（１）記載の、有機溶媒又は有機水溶液吸液剤、
（３）２官能性以上のモノマーがメチレンビスアクリルアミドである、上記（１）記載の、有機溶媒又は有機水溶液吸液剤、
（４）一般式（１）で表されるアルキル（メタ）アクリルアミドがジメチルアクリルアミドであり、かつ２官能性以上のモノマーがメチレンビスアクリルアミドである、上記（１）記載の有機溶媒又は有機水溶液吸液剤、
を提供するものである。
The present inventors have found that the problem can be solved by copolymerizing a monomer having a specific structure and a crosslinking agent, and have completed the present invention.
That is, the present invention
(1) General formula (1) (In the formula, R 1 is a hydrogen atom or a methyl group, R 2 and R 3 are C n H (2n + 1) groups (where n represents a natural number of 1 or more and 4 or less). An organic solvent or an organic aqueous solution absorbent, characterized by containing a copolymer obtained by copolymerizing an alkyl (meth) acrylamide represented by (2) and a bifunctional or higher monomer.
(2) The organic solvent or organic aqueous solution absorbent according to (1) above, wherein the alkyl (meth) acrylamide represented by the general formula (1) is dimethylacrylamide,
(3) The organic solvent or the organic aqueous solution absorbent according to (1) above, wherein the bifunctional or higher functional monomer is methylenebisacrylamide,
(4) The organic solvent or the organic aqueous solution absorbent according to the above (1), wherein the alkyl (meth) acrylamide represented by the general formula (1) is dimethylacrylamide, and the bifunctional or higher monomer is methylenebisacrylamide. ,
Is to provide.
本発明の吸液剤は、従来吸液が困難であった有機溶媒及び有機水溶液を効果的に吸液することが出来ると共に、有機溶媒及び有機水溶液吸液後、ゲルは充分な強度（保形性）を有し、保液性に優れている。 The liquid-absorbing agent of the present invention can effectively absorb an organic solvent and an organic aqueous solution that have been difficult to absorb, and the gel has sufficient strength (shape retention) after absorbing the organic solvent and the organic aqueous solution. ) And has excellent liquid retention.
以下、本発明についてさらに詳しく説明する。
本発明で用いられるアルキル（メタ）アクリルアミドは、上記一般式（１）で表され、Ｒ１が水素原子又はメチル基、Ｒ２及びＲ３がＣ１〜Ｃ４の低級アルキル基であり、具体的には、ジメチルアクリルアミド、ジメチル（メタ）アクリルアミド、ジエチルアクリルアミド、ジエチル（メタ）アクリルアミド、メチルエチルアクリルアミド、メチルエチル（メタ）アクリルアミド、ジプロピルアクリルアミド、ジプロピル（メタ）アクリルアミド、ジブチルアクリルアミド、ジブチル（メタ）アクリルアミド等が挙げられる。
これらのモノマーは親水基であるアミド基と同時に疎水性であるジアルキル基を有するので、親水性−疎水性のバランスに優れ、その為有機溶媒及び有機水溶液に対し親和性を発現する事が出来るものと考える。
Hereinafter, the present invention will be described in more detail.
The alkyl (meth) acrylamide used in the present invention is represented by the above general formula (1), R 1 is a hydrogen atom or a methyl group, R 2 and R 3 are C 1 to C 4 lower alkyl groups, Dimethylacrylamide, dimethyl (meth) acrylamide, diethylacrylamide, diethyl (meth) acrylamide, methylethylacrylamide, methylethyl (meth) acrylamide, dipropylacrylamide, dipropyl (meth) acrylamide, dibutylacrylamide, dibutyl (meth) Examples include acrylamide.
These monomers have a hydrophilic diamide group at the same time as an amide group which is a hydrophilic group, so that they have an excellent hydrophilic-hydrophobic balance, and therefore can exhibit affinity for organic solvents and aqueous solutions. I think.
これらのアルキル（メタ）アクリルアミドは、２官能性以上のモノマーと共重合し架橋ゲルを形成することにより、ネットワーク内に有機溶媒及び有機水溶液を効果的に吸液することが出来るようになる。
アルキル（メタ）アクリルアミドと２官能性以上のモノマーの組成比は任意であるが、通常、アルキル（メタ）アクリルアミド：２官能性以上のモノマー＝９９．９９９〜９０．０００：０．００１〜１０．０００（重量比）が好ましい。２官能性以上のモノマーの添加量が１０（重量比）より多くなると、架橋密度が高くなり過ぎ吸液量が低下すると共に、未反応の２官能性以上のモノマーが残り好ましくない。逆に０．００１（重量比）未満となるとアルキル（メタ）アクリルアミドが架橋されていない未架橋のリニアーポリマーが多くなり、有機溶媒及び有機水溶液吸液後のゲル強度が保てなくなり好ましくない。
２官能性以上のモノマーは架橋剤と呼ばれるものであり、例えば、メチレンビスアクリルアミド、エチレングリコールジアクリレート、ビニルアクリルアミド、ジエチレングリコールジアクリレート、トリメチロールプロパントリアクリレート等が例示されるがこの限りではない。
These alkyl (meth) acrylamides can effectively absorb an organic solvent and an organic aqueous solution in the network by copolymerizing with a bifunctional or higher monomer to form a crosslinked gel.
The composition ratio of the alkyl (meth) acrylamide and the bifunctional or higher monomer is arbitrary, but usually the alkyl (meth) acrylamide: bifunctional or higher monomer = 99.999 to 90.000: 0.001 to 10. 000 (weight ratio) is preferred. When the addition amount of the bifunctional or higher monomer exceeds 10 (weight ratio), the crosslinking density becomes too high and the liquid absorption decreases, and the unreacted bifunctional or higher monomer remains undesirably. Conversely, when it is less than 0.001 (weight ratio), the amount of uncrosslinked linear polymer in which alkyl (meth) acrylamide is not crosslinked increases, and the gel strength after absorbing the organic solvent and the organic aqueous solution cannot be maintained, which is not preferable.
The bifunctional or higher functional monomer is called a crosslinking agent, and examples thereof include, but are not limited to, methylene bisacrylamide, ethylene glycol diacrylate, vinyl acrylamide, diethylene glycol diacrylate, trimethylolpropane triacrylate, and the like.
本発明において、アルキル（メタ）アクリルアミドとしては、特に分子当たりの吸液量が相対的に高く、生成ゲルの透明性が高いジメチルアクリルアミドが好適にもちいられ、また、２官能性以上のモノマーとしては、アルキル（メタ）アクリルアミドとの共重合性が良い物が好ましく、例えば、ジメチルアクリルアミドに対しては構造に同じアミド基を有するメチレンビスアクリルアミドが特に好ましい。 In the present invention, as the alkyl (meth) acrylamide, dimethylacrylamide having a relatively high liquid absorption amount per molecule and a high transparency of the resulting gel is preferably used. Those having good copolymerizability with alkyl (meth) acrylamide are preferred. For example, methylenebisacrylamide having the same amide group in the structure is particularly preferred for dimethylacrylamide.
アルキル（メタ）アクリルアミドと２官能性以上のモノマーの共重合は、例えば、溶液重合、沈殿重合、懸濁重合等のラジカル重合にて得ることができる。重合開始剤、反応条件等は公知の条件で十分である。
共重合体は、反応終了後、溶媒を除去し、乾燥することにより容易に単離される。
The copolymerization of an alkyl (meth) acrylamide and a bifunctional or higher monomer can be obtained, for example, by radical polymerization such as solution polymerization, precipitation polymerization or suspension polymerization. Known conditions are sufficient for the polymerization initiator, reaction conditions, and the like.
After completion of the reaction, the copolymer is easily isolated by removing the solvent and drying.
本発明の有機及び有機溶媒水溶液吸液剤においては、架橋して得られるゲル吸収性能を損なわない範囲で、他のモノマーを共重合することができる。
これら他のモノマーとしては、共重合体の親溶媒性を損なわない範囲で得られる吸液体の粘着性や柔軟性を上げるためのものとして、メチルアクリレート、メチルビニルエーテル、メチルメタクリレート、メトキシエチルアクリレート、アクリロニトリル、酢酸ビニル、プロピオン酸ビニル等が例示される。又、有機及び有機水水溶液に対する吸液量の向上及び吸収速度の向上の為に（メタ）アクリル酸、２−アクリルアミド−２メチルプロパンスルホン酸及びその塩類のイオン性モノマーを共重合する事も可能である。
In the organic and organic solvent aqueous solution absorbent of the present invention, other monomers can be copolymerized within a range that does not impair the gel absorption performance obtained by crosslinking.
These other monomers include methyl acrylate, methyl vinyl ether, methyl methacrylate, methoxyethyl acrylate, and acrylonitrile to increase the adhesiveness and flexibility of the liquid absorption obtained within the range that does not impair the solvophilicity of the copolymer. , Vinyl acetate, vinyl propionate and the like. It is also possible to copolymerize ionic monomers such as (meth) acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and their salts in order to improve the absorption capacity and the absorption rate for organic and organic water solutions. It is.
本発明の吸液剤は、例えば、共重合体を粉砕し粉末化することにより、保管、ハンドリングが容易となり、そのまま、あるいは他の基材と混合して、各種用途に好適に使用することができる。 The liquid-absorbing agent of the present invention, for example, can be stored and handled easily by pulverizing and pulverizing the copolymer, and can be suitably used for various applications as it is or mixed with other base materials. .
以下に実施例により、本発明を詳細に、より具体的に説明するが、本発明は実施例のみに限定されるものではない。
実施例１ ジメチルアクリルアミドゲルの合成
１Ｌガラス製セパラブルフラスコに温度計、窒素導入管、排気管を設けた重合容器を、予め５℃の恒温槽に浸漬した。ジメチルアクリルアミド１０５重量部、メチレンビスアクリルアミド０．１３重量部、純水５９５重量部を均一に溶解し恒温槽に浸漬しておいた重合容器内に移し替え、攪拌下、窒素で３０分脱気を行った後、重合開始剤として６９％パーブチル０．１４重量部、ロンガリット０．１６重量部、ＶＡ０４４（和光純薬）０．１７重量部を各々純水に溶解した溶液を添加し重合を行った。
重合開始剤を添加し増粘が始まった時点で、重合容器を高温槽から引き上げ、室温で１２時間放置した。重合反応終了後、生成したゲルをトレーに並べ、１００℃で１２時間乾燥を行い、粉砕器で粉砕する事により粉末状のゲルを得た。
The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the examples.
Example 1 Synthesis of dimethylacrylamide gel A polymerization vessel in which a 1 L glass separable flask was provided with a thermometer, a nitrogen introduction tube, and an exhaust tube was previously immersed in a thermostat at 5 ° C. Transfer 105 parts by weight of dimethylacrylamide, 0.13 parts by weight of methylenebisacrylamide and 595 parts by weight of pure water into a polymerization vessel that has been uniformly dissolved and immersed in a thermostatic bath, and deaerate with nitrogen for 30 minutes under stirring. After the polymerization, 0.14 parts by weight of 69% perbutyl, 0.16 parts by weight of Rongalite, and 0.17 parts by weight of VA044 (Wako Pure Chemical Industries, Ltd.) were each added as a polymerization initiator to perform polymerization. .
When the polymerization initiator was added and thickening started, the polymerization vessel was lifted from the high temperature bath and allowed to stand at room temperature for 12 hours. After the completion of the polymerization reaction, the produced gel was arranged in a tray, dried at 100 ° C. for 12 hours, and pulverized with a pulverizer to obtain a powdered gel.
評価例１ 吸液試験
実施例１で重合したジメチルアクリルアミドゲル０．３ｇをティーパックに入れ、５００ｍｌの蓋付きの容器に移し、有機溶媒若しくは有機水溶液５００ｍｌを注ぎ、スタラーで緩やかに攪拌しながら１２時間吸液させた。吸液後の重量を測定することにより吸液倍率を計算した。表１に種々の有機溶媒及び有機水溶液に対するジメチルアクリルアミドゲルの吸液倍率を示した。吸液後のゲルは何れも強度を有する固形状で指で圧力を掛けても有機溶媒又は有機水溶液が滲みだして来る事はなかった。 又、吸液後の透明性も高く、芳香剤や消臭剤の基材として有効に活用できるものと考えられる。
Evaluation Example 1 Liquid Absorption Test 0.3 g of the dimethylacrylamide gel polymerized in Example 1 was placed in a tea pack, transferred to a 500 ml container with a lid, poured with 500 ml of an organic solvent or an organic aqueous solution, and stirred gently with a stirrer. The liquid was absorbed for a time. The liquid absorption ratio was calculated by measuring the weight after liquid absorption. Table 1 shows the absorption capacity of dimethylacrylamide gel for various organic solvents and organic aqueous solutions. The gels after the liquid absorption were solid in strength, and even when pressure was applied with a finger, the organic solvent or the organic aqueous solution did not exude. Moreover, the transparency after liquid absorption is high, and it is considered that it can be effectively used as a base material for fragrances and deodorants.
比較評価例１
評価例１において、ジメチルアクリルアミドゲルにかえて高分子吸収体であるポリアクリル酸ソーダを用いた以外は評価例１と同様の方法で吸液試験を行った。結果を表１に示す。
殆どの有機溶媒を吸液できず、吸液しても極僅かであった。
Comparative evaluation example 1
In Evaluation Example 1, a liquid absorption test was conducted in the same manner as in Evaluation Example 1 except that polyacrylic acid sodium which was a polymer absorber was used instead of dimethylacrylamide gel. The results are shown in Table 1.
Most organic solvents could not be absorbed, and even when absorbed, there was very little.
比較評価例２
評価例１において、ジメチルアクリルアミドゲルにかえてＰ−Ｎ−ビニルアセトアミドゲル（架橋体）を用いた以外は評価例１と同様の方法で吸液試験を行った。結果を表１に示す。
有機溶媒を吸液できたが、吸液量はジメチルアクリルアミドゲルに比べて少なく、また、ＴＨＦ、アセトニトリルは全く吸液できなかった。
Comparative evaluation example 2
In Evaluation Example 1, a liquid absorption test was performed in the same manner as in Evaluation Example 1 except that PN-vinylacetamide gel (crosslinked product) was used instead of dimethylacrylamide gel. The results are shown in Table 1.
Although the organic solvent could be absorbed, the amount absorbed was smaller than that of the dimethylacrylamide gel, and THF and acetonitrile could not be absorbed at all.
本発明の吸収剤は、アルコール（１価アルコール、脂肪族多価アルコール、２個以上の水酸基を有する重縮合体）及びその水溶液、ＤＭＦ、ＤＭＳＯ、ＴＨＦ、アセトニトリル、ホルムアミド等有機溶媒を吸収することができるとともに、吸収後、十分なゲル強度と保液性を有するため、蓄熱材、芳香剤、消臭剤、各種有機廃液吸液剤、水溶性塗料吸液剤、有機廃液漏洩時の固化剤、アルコール廃液固化剤、緑化用肥料保水剤等の基材として有効に利用する事ができる。 The absorbent of the present invention absorbs an organic solvent such as alcohol (monohydric alcohol, aliphatic polyhydric alcohol, polycondensate having two or more hydroxyl groups) and an aqueous solution thereof, DMF, DMSO, THF, acetonitrile, formamide, and the like. In addition, it has sufficient gel strength and liquid retention after absorption. It can be effectively used as a base material for waste liquid solidifying agents, fertilizer water retention agents for greening, and the like.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH061886A (en) * | 1992-06-19 | 1994-01-11 | C I Kasei Co Ltd | Water-swellable rubber |
| JPH0680889A (en) * | 1992-09-02 | 1994-03-22 | Nippon Shokubai Co Ltd | Production of granular oil absorbing agent |
| JPH0680955A (en) * | 1992-09-02 | 1994-03-22 | Nippon Shokubai Co Ltd | Production of particulate oil absorbent |
| JP2003151632A (en) * | 2001-11-14 | 2003-05-23 | Nitto Denko Corp | Gel electrolyte and nonaqueous electrolyte battery using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH061886A (en) * | 1992-06-19 | 1994-01-11 | C I Kasei Co Ltd | Water-swellable rubber |
| JPH0680889A (en) * | 1992-09-02 | 1994-03-22 | Nippon Shokubai Co Ltd | Production of granular oil absorbing agent |
| JPH0680955A (en) * | 1992-09-02 | 1994-03-22 | Nippon Shokubai Co Ltd | Production of particulate oil absorbent |
| JP2003151632A (en) * | 2001-11-14 | 2003-05-23 | Nitto Denko Corp | Gel electrolyte and nonaqueous electrolyte battery using the same |
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