JP5339452B2 - Ionic liquid and polymer treatment agent comprising this ionic liquid - Google Patents
Ionic liquid and polymer treatment agent comprising this ionic liquid Download PDFInfo
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- JP5339452B2 JP5339452B2 JP2009511883A JP2009511883A JP5339452B2 JP 5339452 B2 JP5339452 B2 JP 5339452B2 JP 2009511883 A JP2009511883 A JP 2009511883A JP 2009511883 A JP2009511883 A JP 2009511883A JP 5339452 B2 JP5339452 B2 JP 5339452B2
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- C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
Description
本発明は、イオン液体およびこのイオン液体からなるポリマー処理剤に関し、さらに詳述すると、４級窒素原子およびこの窒素原子上にアルコキシアルキル基を有するカチオンと、リン酸系アニオンとからなるイオン液体およびこのイオン液体からなるポリマー処理剤に関する。 The present invention relates to an ionic liquid and a polymer treating agent comprising the ionic liquid. More specifically, the present invention relates to an ionic liquid comprising a quaternary nitrogen atom, a cation having an alkoxyalkyl group on the nitrogen atom, and a phosphate anion, and The present invention relates to a polymer treating agent comprising this ionic liquid.
従来、イオン液体に、セルロース、絹、ウール等の高分子物質が溶解することが知られている（非特許文献１：JACS, 2002, vol.124, p.4274-4275、非特許文献２：JACS, 2004, vol.126, p.14350-14351、非特許文献３：Green Chem., 2005, vol.7, p.606-608参照）。
中でも、セルロースについては、セルロースのイオン液体溶液を利用した再生や、化学修飾、表面処理などが試みられている。Conventionally, it is known that polymer substances such as cellulose, silk, and wool dissolve in an ionic liquid (Non-patent Document 1: JACS, 2002, vol.124, p.4274-4275, Non-patent Document 2: JACS, 2004, vol. 126, p. 14350-14351, Non-Patent Document 3: Green Chem., 2005, vol. 7, p. 606-608).
In particular, for cellulose, attempts have been made to regenerate, chemically modify, surface-treat, etc. using an ionic liquid solution of cellulose.
例えば、特許文献１（特表２００５−５０６４０１号公報）には、実質的に水を含まない１−ブチル−３−メチルイミダゾリウムクロライドなどのイオン液体中にセルロースを溶解させてセルロース溶液を調製し、これに水を加えてセルロースを再生させる方法が開示されている。
特許文献２（国際公開第２００５／０５４２９８号パンフレット）には、１−ブチル−３−メチルイミダゾリウムクロライドに代表されるイオン液体にセルロースを溶解し、セルロースの水酸基をエーテル化する手法が開示されている。
特許文献３（特表２００５−５３０９１０号公報）には、イオン液体を含む布地処理剤で処理されたセルロース系布地は、機能的または美観的に優れた外観を示し、繊維強化効果が発揮され得ることが開示されている。For example, in Patent Document 1 (Japanese Patent Publication No. 2005-506401), a cellulose solution is prepared by dissolving cellulose in an ionic liquid such as 1-butyl-3-methylimidazolium chloride substantially free of water. A method for regenerating cellulose by adding water is disclosed.
Patent Document 2 (International Publication No. 2005/054298) discloses a technique in which cellulose is dissolved in an ionic liquid typified by 1-butyl-3-methylimidazolium chloride, and the hydroxyl group of cellulose is etherified. Yes.
In patent document 3 (Japanese translations of PCT publication No. 2005-530910 gazette), the cellulosic fabric processed with the fabric processing agent containing an ionic liquid shows the functional or aesthetic appearance outstanding, and the fiber reinforcement effect can be exhibited. It is disclosed.
特許文献４（特開２００２−３４７８号公報）には、窒素原子上にアルコキシアルキル基を有するイミダゾリウム系イオン液体が、合成高分子、蛋白質、多糖、糖誘導体の溶解能を有することが開示されている。
特許文献５（特開２００６−１３７６７７号公報）には、カルボン酸系アニオンを有する高極性非ハロゲン系イオン液体が、セルロース、キチン、キトサン等の難溶性多糖類の溶解能を有することが開示されている。Patent Document 4 (Japanese Patent Laid-Open No. 2002-3478) discloses that an imidazolium-based ionic liquid having an alkoxyalkyl group on a nitrogen atom has the ability to dissolve synthetic polymers, proteins, polysaccharides, and sugar derivatives. ing.
Patent Document 5 (Japanese Patent Application Laid-Open No. 2006-137777) discloses that a highly polar non-halogen ionic liquid having a carboxylic acid anion has the ability to dissolve poorly soluble polysaccharides such as cellulose, chitin, and chitosan. ing.
しかしながら、上記各文献に開示されているような、セルロース等のポリマーの溶解能を有するイオン液体のほとんどが室温で固体であるため、ポリマーを室温で処理することは困難である。このため、イオン液体が溶融するような比較的高い温度で処理する必要があり、エネルギーコストが大きくなるという問題がある。しかも、処理温度を高くすると、被処理物であるポリマーの分子量が低下する場合があり、その結果、処理後のポリマーの物性が低下するという問題もある。
また、従来のセルロースを溶解するイオン液体は、室温で液体であっても粘度が高いため、液体としての取扱い性に劣るうえに、被処理物との接触およびその後の被処理物内部への浸透などに時間を要するという問題もある。However, since most of the ionic liquids having the ability to dissolve polymers such as cellulose as disclosed in the above documents are solid at room temperature, it is difficult to treat the polymer at room temperature. For this reason, it is necessary to perform the treatment at a relatively high temperature at which the ionic liquid melts, and there is a problem that the energy cost increases. In addition, when the treatment temperature is increased, the molecular weight of the polymer to be treated may decrease, and as a result, there is a problem that the physical properties of the polymer after treatment are lowered.
In addition, conventional ionic liquids that dissolve cellulose have high viscosity even at room temperature, so that they are not easy to handle as liquids. In addition, they come into contact with the object to be processed and then penetrate into the object to be processed. There is also a problem that it takes time.
なお、特許文献６（仏国特許出願公開第２４８６０７９号明細書）および非特許文献４（Green Chem., 2007, vol.9, p.233-242）には、イミダゾリウムカチオンと、特定のリン酸系アニオンとからなるイオン液体が開示されているが、このイオン液体がセルロースなどの溶解能を有することについては開示されていない。 Patent Document 6 (French Patent Application Publication No. 2486079) and Non-Patent Document 4 (Green Chem., 2007, vol. 9, p.233-242) include an imidazolium cation and a specific phosphorus. Although an ionic liquid composed of an acid anion is disclosed, it is not disclosed that the ionic liquid has a dissolving ability such as cellulose.
本発明は、このような事情に鑑みてなされたものであり、室温付近で天然高分子等の各種ポリマーを溶解することが可能であり、かつ、粘度が比較的低く液体としての取扱い性および被処理物の処理性の良好なイオン液体およびこのイオン液体からなるポリマー処理剤を提供することを目的とする。 The present invention has been made in view of such circumstances, and is capable of dissolving various polymers such as natural polymers near room temperature, has a relatively low viscosity, and is easy to handle as a liquid. It is an object of the present invention to provide an ionic liquid having a good treatability of a treated product and a polymer treating agent comprising the ionic liquid.
本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、４級窒素原子およびこの窒素原子上にアルコキシアルキル基を有するカチオンと、リン酸系アニオンとからなるイオン液体が、室温（２５℃）付近の温度で液体であり、かつ、この温度で比較的低粘度であること、および室温（２５℃）付近でセルロースなどのポリマーを溶解し得ることを見出し、本発明を完成した。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an ionic liquid comprising a quaternary nitrogen atom, a cation having an alkoxyalkyl group on the nitrogen atom, and a phosphate anion is room temperature ( The present invention was completed by finding that it is liquid at a temperature around 25 ° C.) and has a relatively low viscosity at this temperature and that it can dissolve polymers such as cellulose around room temperature (25 ° C.).
すなわち、本発明は、
１． 式（１）で示される４級アンモニウムカチオンと、（ＣＨ3Ｏ）（Ｒ）ＰＯ2 -（Ｒは、水素原子、メチル基、またはメトキシ基を示す。）とからなるイオン液体、
Ｒ1Ｒ2Ｒ3Ｒ4Ｎ+ ・・・（１）
〔式中、Ｒ1、Ｒ2、Ｒ3およびＲ4は、互いに同一でも異なっていてもよい、炭素数１〜１２の直鎖もしくは分岐のアルキル基、または−（ＣＨ2）n−ＯＲ5で示されるアルコキシアルキル基（Ｒ5は、メチル基またはエチル基を示し、ｎは、１または２である。）を示し（ただし、Ｒ1、Ｒ2、Ｒ3およびＲ4の少なくとも１つは前記アルコキシアルキル基である。）、これらＲ1、Ｒ2、Ｒ3およびＲ4のいずれか２個の基が窒素原子とともに環（当該環中にその他のヘテロ原子を含んでいてもよい。）を形成していてもよい。〕
２． 前記Ｒ1、Ｒ2、Ｒ3およびＲ4が、互いに同一でも異なっていてもよい、炭素数１〜８の直鎖アルキル基、または−（ＣＨ2）n−ＯＲ5で示されるアルコキシアルキル基（Ｒ5はメチル基またはエチル基を示し、ｎは１または２である。）を示し（ただし、Ｒ1、Ｒ2、Ｒ3およびＲ4の少なくとも１つは前記アルコキシアルキル基である。）、これらＲ1、Ｒ2、Ｒ3およびＲ4のいずれか２個の基が窒素原子とともに環（当該環中にその他のヘテロ原子を含んでいてもよい。）を形成していてもよい１のイオン液体、
３． 前記カチオンが、式（２）で示される１または２のイオン液体、
４． 前記カチオンが、式（３）で示される１または２のイオン液体、
５． １〜４のいずれかのイオン液体からなるポリマー処理剤、
６． 天然高分子化合物の処理剤である５のポリマー処理剤、
７． 前記天然高分子化合物が、セルロースである６のポリマー処理剤、
８． 表面処理剤、膨潤剤または溶解剤である５〜７のいずれかのポリマー処理剤、
９． ５〜８のいずれかのポリマー処理剤を用いるポリマー処理方法、
１０． １〜４のいずれかのイオン液体と、１種または２種以上のポリマーとを含み、このポリマーが前記イオン液体に溶解しているドープ、
１１． ５のポリマー処理剤と、１種または２種以上のポリマーとを含み、このポリマーが前記ポリマー処理剤に溶解しているドープ、
１２． １０もしくは１１のドープに、前記イオン液体に相溶し、かつ、前記ポリマーの溶解能を実質的に有しない媒体を加え、または１０もしくは１１のドープを、前記イオン液体に相溶し、かつ、前記ポリマーの溶解能を実質的に有しない媒体に加えることを特徴とする再生ポリマーの製造方法
を提供する。
That is, the present invention
1. An ionic liquid comprising a quaternary ammonium cation represented by the formula (1) and (CH 3 O) (R) PO 2 − (R represents a hydrogen atom, a methyl group or a methoxy group);
R 1 R 2 R 3 R 4 N + (1)
[Wherein R 1 , R 2 , R 3 and R 4 may be the same as or different from each other, a linear or branched alkyl group having 1 to 12 carbon atoms, or — (CH 2 ) n —OR 5. (Wherein R 5 represents a methyl group or an ethyl group, and n is 1 or 2), provided that at least one of R 1 , R 2 , R 3 and R 4 is Any one of R 1 , R 2 , R 3 and R 4 together with a nitrogen atom in a ring (other heteroatoms may be contained in the ring). May be formed. ]
2. R 1 , R 2 , R 3 and R 4 may be the same as or different from each other, a linear alkyl group having 1 to 8 carbon atoms, or an alkoxyalkyl group represented by — (CH 2 ) n —OR 5 (R 5 represents a methyl group or an ethyl group, and n is 1 or 2.) (However, at least one of R 1 , R 2 , R 3, and R 4 is the alkoxyalkyl group.) , Any two groups of R 1 , R 2 , R 3 and R 4 may form a ring (which may contain other heteroatoms in the ring) together with the
3. The cation is 1 or 2 ionic liquid represented by formula (2),
4). The cation is 1 or 2 ionic liquid represented by formula (3),
5. A polymer treatment agent comprising any one of
6). 5 polymer treatment agents that are treatment agents for natural polymer compounds ,
7). 6. The polymer treatment agent, wherein the natural polymer compound is cellulose ,
8). A polymer treatment agent according to any one of 5 to 7 which is a surface treatment agent, a swelling agent or a solubilizer ;
9. A polymer treatment method using any of the polymer treating agents of 5 to 8 ,
10. A dope comprising any one of
11. A dope comprising 5 polymer treating agents and one or more polymers, wherein the polymer is dissolved in the polymer treating agent ,
12 Adding a medium compatible with the ionic liquid to the 10 or 11 dope and having substantially no ability to dissolve the polymer, or compatible with the 10 or 11 dope in the ionic liquid; and Provided is a method for producing a regenerated polymer, which is added to a medium having substantially no ability to dissolve the polymer .
本発明に係るイオン液体は、４級窒素原子およびこの窒素原子上にアルコキシアルキル基を有するカチオンと、リン酸系アニオンとからなるものであるため、室温付近で液体状態を示し、かつ、比較的低粘度である。したがって、従来のイオン液体では不可能であった室温付近でのポリマーの処理が可能となる。
また、このイオン液体は、カルボン酸系アニオンからなるイオン液体に比べて熱安定性および保存安定性に優れているとともに、合成が容易であるという利点もある。
本発明のイオン液体は、従来のセルロース溶解可能なイオン液体よりも比較的粘度が低いことから取扱い性に優れるばかりでなく、セルロースをはじめとする各種ポリマーの溶解性に優れる。
さらに、本発明のイオン液体は、各種ポリマーを溶解し得るため、このイオン液体と複数種の高分子物質とを含むドープを調製し、これから、ポリマーを再生させることで、従来にないブレンドポリマーの調製が可能となる。Since the ionic liquid according to the present invention is composed of a quaternary nitrogen atom, a cation having an alkoxyalkyl group on the nitrogen atom, and a phosphate anion, it exhibits a liquid state near room temperature and is relatively Low viscosity. Therefore, it becomes possible to process the polymer near room temperature, which is impossible with conventional ionic liquids.
In addition, this ionic liquid is superior in thermal stability and storage stability as compared to an ionic liquid composed of a carboxylic acid anion, and has an advantage that synthesis is easy.
Since the ionic liquid of the present invention has a relatively lower viscosity than the conventional ionic liquid capable of dissolving cellulose, it not only has excellent handleability but also excellent solubility of various polymers including cellulose.
Furthermore, since the ionic liquid of the present invention can dissolve various polymers, a dope containing this ionic liquid and a plurality of types of polymer substances is prepared, and from this, the polymer is regenerated, so that an unprecedented blend polymer can be obtained. Preparation becomes possible.
以下、本発明についてさらに詳しく説明する。
本発明に係るイオン液体は、４級窒素原子およびこの窒素原子上にアルコキシアルキル基を有する所定のカチオンと、（ＣＨ3Ｏ）（Ｒ）ＰＯ2 -（Ｒは、水素原子、メチル基、またはメトキシ基を示す。）からなるものである。
一般的にイオン液体とは、１００℃以下で流動性があり、完全にイオンから成る液体をいうが、本発明のアニオンを有する四級塩はそのほとんどが室温（２５℃）付近で液状を示す。Hereinafter, the present invention will be described in more detail.
The ionic liquid according to the present invention includes a quaternary nitrogen atom and a predetermined cation having an alkoxyalkyl group on the nitrogen atom, and (CH 3 O) (R) PO 2 − (R is a hydrogen atom, a methyl group, or A methoxy group).
In general, an ionic liquid is a liquid that is fluid at 100 ° C. or lower and is completely composed of ions, but most of the quaternary salts having anions of the present invention are liquid at room temperature (25 ° C.). .
本発明のイオン液体を構成するカチオンとしては、４級窒素原子およびこの窒素原子上にアルコキシアルキル基を有するカチオンであればよく、例えば、式（１）で示されるものが挙げられる。
Ｒ1Ｒ2Ｒ3Ｒ4Ｎ+ ・・・（１）
〔式中、Ｒ1、Ｒ2、Ｒ3およびＲ4は、互いに同一でも異なっていてもよい、炭素数１〜１２の直鎖もしくは分岐のアルキル基、または−（ＣＨ2）n−ＯＲ5で示されるアルコキシアルキル基（Ｒ5は、メチル基またはエチル基を示し、ｎは、１または２である。）を示し（ただし、Ｒ1、Ｒ2、Ｒ3およびＲ4の少なくとも１つは前記アルコキシアルキル基である。）、これらＲ1、Ｒ2、Ｒ3およびＲ4のいずれか２個の基が窒素原子とともに環（当該環中にその他のヘテロ原子を含んでいてもよい。）を形成していてもよい。〕The cation constituting the ionic liquid of the present invention may be a cation having a quaternary nitrogen atom and an alkoxyalkyl group on the nitrogen atom, and examples thereof include those represented by the formula (1).
R 1 R 2 R 3 R 4 N + (1)
[Wherein R 1 , R 2 , R 3 and R 4 may be the same as or different from each other, a linear or branched alkyl group having 1 to 12 carbon atoms, or — (CH 2 ) n —OR 5. (Wherein R 5 represents a methyl group or an ethyl group, and n is 1 or 2), provided that at least one of R 1 , R 2 , R 3 and R 4 is Any one of R 1 , R 2 , R 3 and R 4 together with a nitrogen atom in a ring (other heteroatoms may be contained in the ring). May be formed. ]
式（１）において、炭素数１〜１２の直鎖または分岐のアルキル基の具体例としては、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｓ−ブチル基、ｔ−ブチル基、２−メチルプロピル基、１，１−ジメチルエチル基、ｎ−ペンチル基、ｓ−ペンチル基、ｔ−ペンチル基、１−メチルブチル基、２−メチルブチル基、３−メチルブチル基、２，２−ジメチルプロピル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基、ｎ−ウンデシル基、ｎ−ドデシル基等が挙げられる。
これらの中でも、ポリマーの溶解・膨潤能を高めるためには、炭素数１〜８の直鎖アルキル基が好ましく、特に、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基等の炭素数１〜５の直鎖アルキル基が好適である。In the formula (1), specific examples of the linear or branched alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, and s-butyl group. T-butyl group, 2-methylpropyl group, 1,1-dimethylethyl group, n-pentyl group, s-pentyl group, t-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, Examples include 2,2-dimethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group and the like.
Among these, in order to improve the dissolution / swelling ability of the polymer, a linear alkyl group having 1 to 8 carbon atoms is preferable, and in particular, the number of carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. 1-5 linear alkyl groups are preferred.
Ｒ5Ｏ−（ＣＨ2）n−で表されるアルコキシアルキル基としては、メトキシまたはエトキシメチル基、メトキシまたはエトキシエチル基が挙げられる。
特に、Ｒ1、Ｒ2、Ｒ3およびＲ4の少なくとも１つが、−（ＣＨ2）n−ＯＲ5で示されるアルコキシアルキル基（Ｒ5およびｎは上記と同じ。）であることが好ましく、特にメトキシメチル基、メトキシエチル基が好ましい。
好適なカチオンとしては、例えば、下記式（２）〜（４）で示されるものが挙げられる。Examples of the alkoxyalkyl group represented by R 5 O— (CH 2 ) n — include a methoxy or ethoxymethyl group and a methoxy or ethoxyethyl group.
In particular, at least one of R 1 , R 2 , R 3 and R 4 is preferably an alkoxyalkyl group represented by — (CH 2 ) n —OR 5 (R 5 and n are as defined above), A methoxymethyl group and a methoxyethyl group are particularly preferable.
As a suitable cation, what is shown by following formula (2)-(4) is mentioned, for example.
式（２）で示されるカチオンの中でも、比較的低融点になること、ポリマーの溶解・膨潤能に優れていることから、Ｎ，Ｎ−ジエチル−Ｎ−メチル−Ｎ−２−メトキシエチルアンモニウムカチオン、Ｎ，Ｎ−ジエチル−Ｎ−メチル−Ｎ−２−メトキシメチルアンモニウムカチオン、Ｎ−エチル−Ｎ，Ｎ−ジメチル−Ｎ−２−メトキシエチルアンモニウムカチオン、Ｎ−エチル−Ｎ，Ｎ−ジメチル−Ｎ−２−メトキシメチルアンモニウムカチオンなどが好適である。 Among the cations represented by the formula (2), the N, N-diethyl-N-methyl-N-2-methoxyethylammonium cation has a relatively low melting point and is excellent in the ability to dissolve and swell the polymer. N, N-diethyl-N-methyl-N-2-methoxymethylammonium cation, N-ethyl-N, N-dimethyl-N-2-methoxyethylammonium cation, N-ethyl-N, N-dimethyl-N A 2-methoxymethylammonium cation or the like is preferable.
式（３）で示されるカチオンの中でも、比較的低融点になること、ポリマーの溶解・膨潤能に優れていることから、Ｎ−メチル−Ｎ−２−メトキシエチルピロリジニウムカチオン、Ｎ−エチル−Ｎ−２−メトキシエチルピロリジニウムカチオン、Ｎ−メチル−Ｎ−２−メトキシメチルピロリジニウムカチオン、Ｎ−エチル−Ｎ−２−メトキシメチルピロリジニウムカチオンなどが好適である。 Among the cations represented by the formula (3), the N-methyl-N-2-methoxyethylpyrrolidinium cation, N-ethyl has a relatively low melting point and is excellent in the ability to dissolve and swell the polymer. -N-2-methoxyethylpyrrolidinium cation, N-methyl-N-2-methoxymethylpyrrolidinium cation, N-ethyl-N-2-methoxymethylpyrrolidinium cation and the like are preferable.
式（４）で示されるカチオンの中でも、比較的低融点になること、ポリマーの溶解・膨潤能に優れていることから、Ｎ−メチル−Ｎ−２−メトキシエチルピペリジニウムカチオン、Ｎ−メチル−Ｎ−２−メトキシエチルモルホリニウムカチオンなどが好適である。 Among the cations represented by the formula (4), N-methyl-N-2-methoxyethylpiperidinium cation, N-methyl has a relatively low melting point and is excellent in the ability to dissolve and swell the polymer. -N-2-methoxyethylmorpholinium cation and the like are preferable.
また、本発明のイオン液体を構成する４級窒素原子およびこの窒素原子上にアルコキシアルキル基を有するカチオンとしては、下記式（５）で示されるものも挙げられる。 Moreover, what is shown by following formula (5) is mentioned as a quaternary nitrogen atom which comprises the ionic liquid of this invention, and a cation which has an alkoxyalkyl group on this nitrogen atom.
式（５）で示されるカチオンの中でも、比較的低融点になること、ポリマーの溶解・膨潤能に優れていることから、１−（２−メトキシエチル）−３−メチルイミダゾリウムカチオン、１−メトキシメチル−３−メチルイミダゾリウムカチオン、１−エチル−３−（２−メトキシエチル）イミダゾリウムカチオン、１−エチル−３−メトキシメチル）イミダゾリウムカチオンなどが好適である。 Among the cations represented by the formula (5), a 1- (2-methoxyethyl) -3-methylimidazolium cation, 1- (2-methoxyethyl) -3-methylimidazolium cation, Methoxymethyl-3-methylimidazolium cation, 1-ethyl-3- (2-methoxyethyl) imidazolium cation, 1-ethyl-3-methoxymethyl) imidazolium cation and the like are preferable.
本発明のイオン液体を構成するアニオンは、（ＣＨ3Ｏ）（Ｒ）ＰＯ2 -（Ｒは、水素原子、メチル基、またはメトキシ基を示す。）であるが、セルロースなどの溶解能に優れることから、Ｒは、水素原子またはメチル基であることが好ましい。The anion constituting the ionic liquid of the present invention is (CH 3 O) (R) PO 2 − (wherein R represents a hydrogen atom, a methyl group, or a methoxy group), but is excellent in solubility of cellulose and the like. Therefore, R is preferably a hydrogen atom or a methyl group.
本発明のポリマー処理剤は、上述したイオン液体からなるものであり、各種ポリマーの表面処理剤、溶解剤、膨潤剤などとして好適に用いることができる。なお、イオン液体は、１種単独で、または２種以上混合してポリマー処理剤とすることができる。
また、上記イオン液体以外のイオン液体や有機溶媒と混合してポリマーの処理剤とすることも可能であり、これらは１種または２種以上添加することも可能である。上記イオン液体以外のイオン液体としては特に制限はなく、また、有機溶媒としてはジメチルホルムアミド、ジメチルスルホキシド、Ｎ−メチルピロリドン等の非プロトン性溶媒がセルロース等のポリマーの溶解を妨げる程度が低いため好ましい。これらの添加量は、セルロース等のポリマーの溶出を供しない程度であれば特に制限は無く、処理剤の粘度低下の度合等を勘案して決めるのが良い。The polymer treatment agent of the present invention comprises the ionic liquid described above, and can be suitably used as a surface treatment agent, a solubilizing agent, a swelling agent, etc. for various polymers. In addition, an ionic liquid can be used individually by 1 type or in mixture of 2 or more types as a polymer processing agent.
Moreover, it is also possible to mix with ionic liquids other than the said ionic liquid, or an organic solvent, and to make a polymer processing agent, and these can also be added 1 type (s) or 2 or more types. The ionic liquid other than the ionic liquid is not particularly limited, and an organic solvent is preferably an aprotic solvent such as dimethylformamide, dimethyl sulfoxide or N-methylpyrrolidone because it has a low degree of hindering dissolution of a polymer such as cellulose. . These addition amounts are not particularly limited as long as they do not cause elution of polymers such as cellulose, and are preferably determined in consideration of the degree of viscosity reduction of the treatment agent.
本発明において、溶解とは、ポリマーが媒体中に均一相として存在するように視認されることをいう。膨潤とは、媒体がポリマーの凝集分子鎖中に浸入し、分子鎖同士の相互作用が緩和されているが、完全に分子鎖の凝集が解かれるまでには至っていない状態をいう。 In the present invention, dissolution means that the polymer is visually recognized as a homogeneous phase in the medium. Swelling refers to a state in which the medium has penetrated into the polymer aggregate molecular chain and the interaction between the molecular chains has been relaxed, but the molecular chain aggregation has not been completely solved.
ポリマー処理剤の粘度は、低い程好ましいが、処理剤のポリマーへの浸透の容易さや、液体としての取扱いの容易さ、連続工程の場合に洗浄層への処理剤の混入を少なくすることなどを考慮すると、３０℃で５０００Ｐａ・ｓ以下であることが好ましく、２０００Ｐａ・ｓ以下であることがより好ましく、１０００Ｐａ・ｓ以下であることが好適である。
なお、本発明のポリマー処理剤には、その効果を発現させる限度においてその他の成分を添加することもできる。その他の成分としては、香料、染料、撥水剤、撥油剤、抗菌剤、防カビ剤などが挙げられる。The viscosity of the polymer treatment agent is preferably as low as possible, but the ease of penetration of the treatment agent into the polymer, the ease of handling as a liquid, and the reduction of contamination of the treatment agent into the cleaning layer in the case of continuous processes, etc. In consideration, it is preferably 5000 Pa · s or less at 30 ° C., more preferably 2000 Pa · s or less, and more preferably 1000 Pa · s or less.
It should be noted that other components can be added to the polymer treating agent of the present invention as long as the effect is exhibited. Examples of other components include fragrances, dyes, water repellents, oil repellents, antibacterial agents, and fungicides.
本発明のポリマー処理剤で処理されるポリマーとしては、上述したイオン液体に溶解または膨潤するものであれば特に限定はなく、例えば、糖鎖もしくはタンパク質等の天然高分子化合物、またはこれらの混合物が挙げられる。
糖鎖としては、セルロース、キチン、キトサンなどが挙げられる。
セルロースとしては、植物由来セルロース、動物由来セルロース、バクテリア由来セルロース、再生セルロースが挙げられる。具体的には、綿、麻、竹、バナナ、月桃、ハイビスカスローゼル、ケナフ、広葉樹パルプ、針葉樹パルプ、ホヤセルロース、バクテリアセルロース、レーヨン、キュプラ、テンセル、イオン液体による再生セルロースなどが挙げられ、イオン液体に溶解，膨潤し得る限り、それらの誘導体でもよい。誘導体としては、例えばセルロースの水酸基をエーテル化またはエステル化した誘導体や、シアノエチル化した誘導体や、カーバメート化した誘導体などが挙げられる。
また、上記ポリマー以外に本発明の処理剤に溶解または膨潤する他成分を含むものであってもよく、例えば、セルロース以外の他成分を含んだ木質系セルロース等も本発明の処理剤で処理できる。その場合は、木質系セルロース等を天然のまま処理してもよいし、予め脱リグニン処理等を行ったものを処理してもよい。
なお、セルロースの結晶構造は任意であり、Ｉ型、ＩＩ型、ＩＩＩ型、ＩＶ型、非晶のいずれか１つの構造またはそれらの組合せからなる構造を有するセルロースを採用できる。また、セルロースの結晶化度に関わらず用いることができる。
タンパク質としては、絹、羊毛、コラーゲン、ケラチン、セリシン、フィブロイン、カゼイン等が挙げられる。
上記ポリマーの構造は任意であり、糸，織物，編物，不織布，紙等の繊維構造物、フィルム、ビーズ、板、ブロックなどの各種構造を採用できる。The polymer to be treated with the polymer treating agent of the present invention is not particularly limited as long as it dissolves or swells in the ionic liquid described above. For example, natural polymer compounds such as sugar chains or proteins, or mixtures thereof Can be mentioned.
Examples of sugar chains include cellulose, chitin, chitosan and the like.
Examples of cellulose include plant-derived cellulose, animal-derived cellulose, bacterial-derived cellulose, and regenerated cellulose. Specific examples include cotton, hemp, bamboo, banana, moon peach, hibiscus rozel, kenaf, hardwood pulp, conifer pulp, squirt cellulose, bacterial cellulose, rayon, cupra, tencel, regenerated cellulose with ionic liquid, etc. Their derivatives may be used as long as they can be dissolved and swelled in a liquid. Examples of the derivative include a derivative obtained by etherifying or esterifying a hydroxyl group of cellulose, a cyanoethylated derivative, a carbamate derivative, and the like.
In addition to the polymer, it may contain other components that dissolve or swell in the treatment agent of the present invention. For example, woody cellulose containing other components other than cellulose can be treated with the treatment agent of the present invention. . In that case, the woody cellulose or the like may be treated as it is, or the one subjected to delignification treatment in advance may be treated.
The crystal structure of cellulose is arbitrary, and cellulose having a structure composed of any one of I-type, II-type, III-type, IV-type, and amorphous structure or a combination thereof can be employed. Further, it can be used regardless of the crystallinity of cellulose.
Examples of proteins include silk, wool, collagen, keratin, sericin, fibroin, and casein.
The structure of the polymer is arbitrary, and various structures such as a fiber structure such as a yarn, a woven fabric, a knitted fabric, a non-woven fabric, and paper, a film, a bead, a plate, and a block can be employed.
また、上記ポリマーは、当該処理剤に溶解または膨潤しない物質を含んでいてもよい。
このような物質としては、アクリル樹脂、ポリカーボネート樹脂、ＡＢＳ樹脂、ポリ乳酸、ポリカプロラクトン、ポリアミド（ナイロン）、ポリスチレンなどの高分子化合物や、ガラス繊維、金属繊維、炭素繊維、ロックウールなどが挙げられる。
なお、これらの物質の含有量は任意であるが、イオン液体に膨潤または溶解するポリマー全体に対して、５〜９５質量％程度が好適である。The polymer may contain a substance that does not dissolve or swell in the treatment agent.
Examples of such substances include acrylic resins, polycarbonate resins, ABS resins, polylactic acid, polycaprolactone, polyamide (nylon), high molecular compounds such as polystyrene, glass fibers, metal fibers, carbon fibers, rock wool, and the like. .
In addition, although content of these substances is arbitrary, about 5-95 mass% is suitable with respect to the whole polymer which swells or melt | dissolves in an ionic liquid.
以上で説明したポリマー処理剤を用いたポリマー処理方法は、当該ポリマー処理剤を、イオン液体に膨潤または溶解するポリマーや、当該ポリマーを含む被処理物と接触させて、（被処理物中の）ポリマーを膨潤または溶解させたり、表面処理したりするものである。
接触方法としては特に制限はなく、ポリマー処理剤中へポリマー（被処理物）を浸漬させたり、ポリマー処理剤を含む槽内にポリマー（被処理物）を通過させたりする方法や、ポリマー（被処理物）へポリマー処理剤を噴霧する方法などが挙げられる。In the polymer processing method using the polymer processing agent described above, the polymer processing agent is brought into contact with a polymer that swells or dissolves in an ionic liquid or a processing object containing the polymer (in the processing object). A polymer is swollen or dissolved, or surface-treated.
There is no particular limitation on the contact method, and a method of immersing a polymer (object to be treated) in a polymer treatment agent or passing a polymer (object to be treated) into a tank containing the polymer treatment agent, or a polymer (object to be treated). For example, a method of spraying a polymer treatment agent onto the treated product) may be used.
接触時間は、所望の効果に応じて適宜決定すればよく、例えば、上記ポリマーを、本発明のポリマー処理剤と長時間接触させることにより、ポリマーは、その内部まで膨潤または溶解する。
この時の接触時間は処理するポリマー（被処理物）の種類にもよるので一概には規定できないが、例えば、微結晶セルロースのような比較的低分子量のセルロースを溶解する場合は、１分から６００分間程度の範囲で適宜調節すればよい。また、木質系セルロースのような他成分を含むセルロースを溶解する場合は、溶解にある程度時間がかかるため、１時間から数週間、場合によっては数ヶ月程度が好ましい。
一方、ポリマーを当該処理剤と短時間接触させることにより、ポリマーはその表面近傍のみが膨潤もしくは溶解する。このような表面処理を行う場合には、所望する表面処理の性状、度合いに応じ、接触時間を０．０１秒から１８０分間程度の範囲で適宜調節すればよい。
接触温度は、ポリマー処理剤が液体状である温度領域であればよい。本発明のイオン液体のほとんどが室温付近で液体であることから、加熱なしにポリマー（被処理物）の処理が可能でエネルギー的に有利である。また、低温であるほどポリマーの分子量低下も少ないと予想され、ポリマーの物性低下を最小限に食い止めることが期待できる。０〜１５０℃程度が好ましく、１５〜６０℃程度がより好ましい。What is necessary is just to determine a contact time suitably according to the desired effect, for example, a polymer swells or melt | dissolves to the inside by making the said polymer contact the polymer processing agent of this invention for a long time.
The contact time at this time cannot be defined unconditionally because it depends on the type of polymer (object to be treated) to be treated. However, for example, when dissolving a relatively low molecular weight cellulose such as microcrystalline cellulose, 1 minute to 600 What is necessary is just to adjust suitably in the range of about minutes. Further, when dissolving cellulose containing other components such as woody cellulose, it takes some time to dissolve, so it is preferably 1 hour to several weeks, and in some cases about several months.
On the other hand, when the polymer is brought into contact with the treatment agent for a short time, only the vicinity of the surface of the polymer swells or dissolves. When such surface treatment is performed, the contact time may be appropriately adjusted within a range of about 0.01 seconds to 180 minutes depending on the desired property and degree of the surface treatment.
The contact temperature may be a temperature range in which the polymer treatment agent is in a liquid state. Since most of the ionic liquids of the present invention are liquids around room temperature, it is possible to treat the polymer (object to be treated) without heating, which is advantageous in terms of energy. In addition, the lower the temperature, the lower the molecular weight of the polymer is expected, and it can be expected that the physical properties of the polymer are reduced to a minimum. About 0-150 degreeC is preferable and about 15-60 degreeC is more preferable.
接触処理後のポリマー（処理物）に残存したポリマー処理剤は、ポリマー処理剤と相溶でかつ処理後のポリマーを溶解・膨潤させない溶液で洗浄することで容易に除去することができる。
このような溶媒としては、例えば、水、メタノール，エタノール等のアルコール類、テトラヒドロフラン，ジオキサン等のエーテル類、アセトン，メチルエチルケトン等のケトン類、アセトニトリル、クロロホルム等が挙げられ、これらは１種単独で、または２種以上混合して用いることができる。
接触処理および必要に応じて行われる洗浄処理後、処理後のポリマー（処理物）を適宜乾燥させればよい。乾燥手法は任意であり、公知の各種方法を用いることができる。具体例としては、ヒートドラム、熱風、赤外線、天日による方法などが挙げられる。The polymer treating agent remaining in the polymer (treated product) after the contact treatment can be easily removed by washing with a solution that is compatible with the polymer treating agent and does not dissolve or swell the treated polymer.
Examples of such a solvent include water, alcohols such as methanol and ethanol, ethers such as tetrahydrofuran and dioxane, ketones such as acetone and methyl ethyl ketone, acetonitrile, chloroform, and the like. Alternatively, two or more kinds can be mixed and used.
After the contact treatment and the washing treatment performed as necessary, the polymer after the treatment (processed product) may be appropriately dried. Any drying method can be used, and various known methods can be used. Specific examples include a heat drum, hot air, infrared rays, and a method using sunlight.
本発明に係るドープは、上述したイオン液体と、ポリマーとを含み、ポリマーがイオン液体に溶解しているものである。この場合、ポリマーは２種以上用いてもよい。
このドープ中のポリマーの含有量は、使用するポリマーの種類にもよるため一概には規定できないが、本発明のドープにおいては、０．１〜５０質量％程度とすることができる。
本発明のドープの調製法は特に限定されるものではなく、上述したイオン液体にポリマーを添加・溶解して調製しても、ポリマーにイオン液体を添加・溶解して調製してもよい。
なお、溶解時に適宜加熱してもよい。The dope according to the present invention includes the ionic liquid described above and a polymer, and the polymer is dissolved in the ionic liquid. In this case, two or more polymers may be used.
The content of the polymer in the dope cannot be defined unconditionally because it depends on the type of polymer used, but in the dope of the present invention, it can be about 0.1 to 50% by mass.
The method for preparing the dope of the present invention is not particularly limited, and the dope may be prepared by adding and dissolving the polymer in the ionic liquid described above or by adding and dissolving the ionic liquid in the polymer.
In addition, you may heat suitably at the time of melt | dissolution.
本発明のドープを用いることで再生ポリマーを製造することができ、特に２種以上のポリマーを含むドープの場合には、これら各ポリマーのブレンドポリマーを製造することができる。既に述べたように、本発明のイオン液体は、室温付近で液体状であるとともに粘度が低く、ポリマーをより低温で溶解し得、ポリマーの物性低下などを起こしにくいものであるため、各種ポリマーの物性の低下が抑制されたブレンド物を容易に得ることができる。 By using the dope of the present invention, a regenerated polymer can be produced. In particular, in the case of a dope containing two or more kinds of polymers, a blend polymer of these polymers can be produced. As already described, the ionic liquid of the present invention is liquid around room temperature, has a low viscosity, can dissolve the polymer at a lower temperature, and is less likely to cause deterioration in physical properties of the polymer. It is possible to easily obtain a blend in which deterioration of physical properties is suppressed.
再生ポリマーや、ブレンドポリマーを製造する具体的手法としては、イオン液体に相溶し、かつ、ポリマーの溶解能を実質的に有しない媒体を本発明のドープに加えたり、イオン液体に相溶し、かつ、ポリマーの溶解能を実質的に有しない媒体に本発明のドープを加えたりすることで再生ポリマーやブレンドポリマーを系内で析出させる手法が挙げられる。 As a specific method for producing a recycled polymer or a blend polymer, a medium compatible with an ionic liquid and having substantially no ability to dissolve the polymer is added to the dope of the present invention, or it is compatible with the ionic liquid. And the method of depositing a reproduction | regeneration polymer and a blend polymer in a system by adding the dope of this invention to the medium which does not have a polymer dissolution ability substantially is mentioned.
ここで、イオン液体に対して相溶し、かつ、ポリマーの溶解能を実質的に有しない媒体の具体例としては、水、メタノール，エタノール等のアルコール類、テトラヒドロフラン，ジオキサン等のエーテル類、アセトン，メチルエチルケトン等のケトン類、アセトニトリル、クロロホルムなどが挙げられ、これらは１種単独で、または２種以上混合して用いることができる。これらの中でも、水、アルコール類が好ましく、環境面を配慮すると水がより好ましい。
なお、「ポリマーの溶解能を実質的に有しない媒体」とは、ポリマーを全く溶解しない媒体という意味ではなく、本発明のドープに加え、その添加量を臨界量以上に増大させた場合にポリマーを析出させることが可能な媒体を意味する。Here, specific examples of the medium that is compatible with the ionic liquid and has substantially no polymer dissolving ability include water, alcohols such as methanol and ethanol, ethers such as tetrahydrofuran and dioxane, acetone, and the like. , Ketones such as methyl ethyl ketone, acetonitrile, chloroform and the like. These may be used alone or in combination of two or more. Among these, water and alcohols are preferable, and water is more preferable in consideration of environmental aspects.
The “medium having substantially no polymer dissolving ability” does not mean a medium that does not dissolve the polymer at all. In addition to the dope of the present invention, the polymer is added when the addition amount is increased to a critical amount or more. Means a medium on which can be deposited.
本発明のドープと上記媒体との使用割合は、ポリマーが析出してくる割合であれば任意であり、また使用する媒体によっても変動するものであるため一概に規定することはできないが、効率的にポリマーを析出させるためには、媒体／ドープの液量比（体積比）は１以上が好ましく、２以上がより好ましく、５以上がさらに好ましい。
なお、ドープ中に媒体を加える方法、媒体中にドープを加える方法は任意である。The use ratio of the dope of the present invention and the above medium is arbitrary as long as the polymer is precipitated, and also varies depending on the medium to be used. In order to precipitate the polymer, the medium / dope liquid volume ratio (volume ratio) is preferably 1 or more, more preferably 2 or more, and even more preferably 5 or more.
In addition, the method of adding a medium in dope and the method of adding dope in a medium are arbitrary.
再生ポリマーやブレンドポリマーの形態は、特に限定されるものではなく、粉状、粒状、塊状、綿状、短繊維状、長繊維状、棒状、スポンジ状、フィルム状等の各種形状とすることができる。
たとえば、ドープを上記媒体に加える手法では、Ｔダイなどを通してドープを媒体中に押し出すなどにより、フィルム状や、長繊維状の再生ポリマーやブレンドポリマーを連続的に得ることもできる。The form of the recycled polymer or blend polymer is not particularly limited, and may be various shapes such as powder, granule, lump, cotton, short fiber, long fiber, rod, sponge, film, etc. it can.
For example, in the method of adding the dope to the medium, a film-like or long-fiber regenerated polymer or blend polymer can be continuously obtained by extruding the dope into the medium through a T die or the like.
以下、合成例、実施例および比較例を挙げて、本発明をより具体的に説明するが、本発明は、下記の実施例に限定されるものではない。
なお、以下の実施例におけるイオン液体の構造確認は、1Ｈ−ＮＭＲ（日本電子（株）製、ＡＬ−４００）を用いて行った。EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
In addition, the structure confirmation of the ionic liquid in the following examples was performed using 1 H-NMR (manufactured by JEOL Ltd., AL-400).
［１］イオン液体の合成
［合成例１］化合物（６）の合成
ジエチルアミン（関東化学（株）製）１００ｍｌと２−メトキシエチルクロライド（関東化学（株）製）８５ｍｌとを混合し、オートクレーブ中、１００℃で２４時間反応させた。このとき、内圧は１．３ｋｇｆ／ｃｍ2（０．１３ＭＰａ）あった。２４時間後、析出した結晶と反応液との混合物に水酸化カリウム（片山化学工業（株）製）５６ｇを溶解した水溶液２００ｍｌを加え、２層に分かれた有機層を分液ロートで分液した。さらに、塩化メチレン（和光純薬工業（株）製）１００ｍｌを加えて抽出する操作を２回行った。分液した有機層をまとめ、飽和食塩水で洗浄した後、炭酸カリウム（和光純薬工業（株）製）を加えて乾燥、減圧濾過した。得られた有機層からエバポレータにて溶媒を留去し、残留分について常圧蒸留を行った。沸点１３５℃付近の留分を１８．９ｇ得た。この化合物が２−メトキシエチルジエチルアミンであることを1Ｈ−ＮＭＲにより確認した。
得られた２−メトキシエチルジエチルアミン１０．０ｇとトリメチルリン酸（東京化成工業（株）製）８．８ｍｌとを室温下で混合し、１００℃で４時間反応させた。
反応液を大量のテトラヒドロフラン（和光純薬工業（株）製）５０ｍｌ中へ投入し、５分間程度激しく攪拌した後、静置した。２層に分離した上層をデカンテーションにより除去した。この操作をさらに２回繰り返した後、残留した下層について攪拌下１００℃で１時間の加熱真空乾燥を行い、室温（２５℃、以下同様）でワイン色を呈した液体状の化合物（６）１６．４５ｇを得た。
合成例１で得られた化合物（６）（Ｎ，Ｎ−ジエチル−Ｎ−メチル−Ｎ−２−メトキシエチルアンモニウム ジメチルリン酸塩：［ＤＥＭＥ］［（ＭｅＯ）2ＰＯ2］）の1Ｈ−ＮＭＲスペクトルを図１に示す。なお、測定は、重ジメチルスルホキシドを溶媒として行った。100 ml of diethylamine (manufactured by Kanto Chemical Co., Ltd.) and 85 ml of 2-methoxyethyl chloride (manufactured by Kanto Chemical Co., Ltd.) were mixed and reacted at 100 ° C. for 24 hours in an autoclave. At this time, the internal pressure was 1.3 kgf / cm 2 (0.13 MPa). After 24 hours, 200 ml of an aqueous solution in which 56 g of potassium hydroxide (manufactured by Katayama Chemical Co., Ltd.) was dissolved was added to the mixture of the precipitated crystals and the reaction solution, and the organic layer separated into two layers was separated with a separating funnel. . Further, 100 ml of methylene chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added and extracted twice. The separated organic layers were combined, washed with saturated brine, dried over potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.), and filtered under reduced pressure. The solvent was distilled off from the obtained organic layer with an evaporator, and the residue was subjected to atmospheric distillation. 18.9 g of a fraction having a boiling point near 135 ° C. was obtained. It was confirmed by 1 H-NMR that this compound was 2-methoxyethyldiethylamine.
10.0 g of the obtained 2-methoxyethyldiethylamine and 8.8 ml of trimethyl phosphoric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed at room temperature and reacted at 100 ° C. for 4 hours.
The reaction solution was put into 50 ml of a large amount of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), stirred vigorously for about 5 minutes, and allowed to stand. The upper layer separated into two layers was removed by decantation. After repeating this operation twice more, the remaining lower layer was heated and vacuum-dried at 100 ° C. for 1 hour with stirring, and a liquid compound (6) 16 having a wine color at room temperature (25 ° C., hereinafter the same). .45 g was obtained.
1 H- of the compound (6) obtained in Synthesis Example 1 (N, N-diethyl-N-methyl-N-2-methoxyethylammonium dimethyl phosphate: [DEME] [(MeO) 2 PO 2 ]) The NMR spectrum is shown in FIG. The measurement was performed using heavy dimethyl sulfoxide as a solvent.
［合成例２］化合物（７）の合成
ジエチルアミンをピロリジン（関東化学（株）製）に、オートクレーブでの反応温度を９０℃に変更した以外は、合成例１とほぼ同様の方法で化合物（７）を合成した。化合物（７）は室温で液状であった。
合成例２で得られた化合物（７）（Ｎ−メチル−Ｎ−２−メトキシエチルピロリジニウム ジメチルリン酸塩：［ＭＥＭＰ］［（ＭｅＯ）2ＰＯ2］）の1Ｈ−ＮＭＲスペクトルを図２に示す。なお、測定は、重ジメチルスルホキシドを溶媒として行った。Compound (7) was synthesized in substantially the same manner as in Synthesis Example 1, except that diethylamine was changed to pyrrolidine (manufactured by Kanto Chemical Co., Inc.) and the reaction temperature in the autoclave was changed to 90 ° C. Compound (7) was liquid at room temperature.
1 H-NMR spectrum of compound (7) (N-methyl-N-2-methoxyethylpyrrolidinium dimethyl phosphate: [MEMP] [(MeO) 2 PO 2 ]) obtained in Synthesis Example 2 It is shown in 2. The measurement was performed using heavy dimethyl sulfoxide as a solvent.
［合成例３］化合物（８）の合成
トリメチルリン酸をジメチルメチルホスホン酸（シグマ−アルドリッチジャパン（株）製）に変更した以外は、合成例１とほぼ同様の方法で化合物（８）を合成した。化合物（８）は室温で液状であった。
合成例３で得られた化合物（８）（Ｎ，Ｎ−ジエチル−Ｎ−メチル−Ｎ−２−メトキシエチルアンモニウム メチルジメチルホスホン酸塩：［ＤＥＭＥ］［（ＭｅＯ）（Ｍｅ）ＰＯ2］）の1Ｈ−ＮＭＲスペクトルを図３に示す。なお、測定は、重ジメチルスルホキシドを溶媒として行った。Compound (8) was synthesized in substantially the same manner as in Synthesis Example 1, except that trimethyl phosphoric acid was changed to dimethylmethylphosphonic acid (manufactured by Sigma-Aldrich Japan). Compound (8) was liquid at room temperature.
Compound (8) obtained in Synthesis Example 3 (N, N-diethyl-N-methyl-N-2-methoxyethylammonium methyldimethylphosphonate: [DEME] [(MeO) (Me) PO 2 ]) The 1 H-NMR spectrum is shown in FIG. The measurement was performed using heavy dimethyl sulfoxide as a solvent.
［合成例４］化合物（９）の合成
トリメチルリン酸をジメチルメチルホスホン酸（シグマ−アルドリッチジャパン（株）製）に変更した以外は、合成例２とほぼ同様の方法で化合物（９）を合成した。化合物は室温で液状であった。
合成例４で得られた化合物（９）（Ｎ−メチル−Ｎ−２−メトキシエチルピロリジニウム メチルジメチルホスホン酸塩：［ＭＥＭＰ］［（ＭｅＯ）（Ｍｅ）ＰＯ2］）の1Ｈ−ＮＭＲスペクトルを図４に示す。なお、測定は、重ジメチルスルホキシドを溶媒として行った。Compound (9) was synthesized in substantially the same manner as in Synthesis Example 2 except that trimethyl phosphoric acid was changed to dimethylmethylphosphonic acid (manufactured by Sigma-Aldrich Japan Co., Ltd.). The compound was liquid at room temperature.
1 H-NMR of compound (9) (N-methyl-N-2-methoxyethylpyrrolidinium methyldimethylphosphonate: [MEMP] [(MeO) (Me) PO 2 ]) obtained in Synthesis Example 4 The spectrum is shown in FIG. The measurement was performed using heavy dimethyl sulfoxide as a solvent.
［合成例５］化合物（１０）の合成
トリメチルリン酸をジメチル亜リン酸（シグマ−アルドリッチジャパン（株）製）に変更した以外は、合成例１とほぼ同様の方法で合成を行った。化合物は室温で液状であった。
合成例５で得られた化合物（１０）（Ｎ，Ｎ−ジエチル−Ｎ−メチル−Ｎ−２−メトキシエチルアンモニウム メチル亜リン酸塩：［ＤＥＭＥ］［（ＭｅＯ）（Ｈ）ＰＯ2］）の1Ｈ−ＮＭＲスペクトルを図５に示す。なお、測定は、重ジメチルスルホキシドを溶媒として行った。The synthesis was performed in substantially the same manner as in Synthesis Example 1 except that trimethyl phosphoric acid was changed to dimethyl phosphorous acid (manufactured by Sigma-Aldrich Japan Co., Ltd.). The compound was liquid at room temperature.
Compound (10) obtained in Synthesis Example 5 (N, N-diethyl-N-methyl-N-2-methoxyethylammonium methyl phosphite: [DEME] [(MeO) (H) PO 2 ]) The 1 H-NMR spectrum is shown in FIG. The measurement was performed using heavy dimethyl sulfoxide as a solvent.
［合成例６］化合物（１１）の合成
トリメチルリン酸をジメチル亜リン酸（シグマ−アルドリッチジャパン（株）製）に変更した以外は、合成例２とほぼ同様の方法で合成を行った。化合物は室温で液状であった。
合成例６で得られた化合物（１１）（Ｎ−メチル−Ｎ−２−メトキシエチルピロリジニウム メチル亜リン酸塩：［ＭＥＭＰ］［（ＭｅＯ）（Ｈ）ＰＯ2］）の1Ｈ−ＮＭＲスペクトルを図６に示す。なお、測定は、重ジメチルスルホキシドを溶媒として行った。Synthesis was performed in substantially the same manner as in Synthesis Example 2 except that trimethyl phosphoric acid was changed to dimethyl phosphorous acid (manufactured by Sigma-Aldrich Japan Co., Ltd.). The compound was liquid at room temperature.
1 H-NMR of compound (11) (N-methyl-N-2-methoxyethylpyrrolidinium methyl phosphite: [MEMP] [(MeO) (H) PO 2 ]) obtained in Synthesis Example 6 The spectrum is shown in FIG. The measurement was performed using heavy dimethyl sulfoxide as a solvent.
［合成例７］化合物（１２）の合成
オートクレーブにイミダゾール２７０ｇ（東京化成工業（株）製）、クロロホルム（関東化学（株）製）４００ｍｌ、２−メトキシエチルクロライド（関東化学（株）製）１８８ｇの順で加え、３００ｒｐｍで攪拌して溶解した後、９０℃、２５０ｒｐｍで１４時間反応させた。このとき、内圧は０．１２ｋｇｆ／ｃｍ2（０．０１２ＭＰａ）であった。
エバポレータにて反応液からクロロホルムを留去後、減圧蒸留にて３ｍｍＨｇ／ｃｍ2における沸点１００℃付近の留分を分取した。この留分はＮ−２−メトキシエチルイミダゾールとイミダゾールとの混合物であったため、留分の一部を取り、シリカゲルクロマトグラフィー（クロロホルム：メタノール＝５０：１）で精製し、Ｎ−２−メトキシエチルイミダゾール３５ｇを得た。構造は1Ｈ−ＮＭＲで確認した。
以後は２−メトキシエチルジエチルアミンを上記で得られたＮ−２−メトキシエチルイミダゾールに、トリメチルリン酸をジメチル亜リン酸にそれぞれ変更した以外は、合成例１とほぼ同様の方法で化合物（１２）を合成した。化合物は室温で液状であった。
合成例７で得られた化合物（１２）（１−メトキシエチル−３−メチルイミダゾリウム メチル亜リン酸塩：［ＭＥＭＩｍ］［（ＭｅＯ）（Ｈ）ＰＯ2］）の1Ｈ−ＮＭＲスペクトルを図７に示す。なお、測定は、重ジメチルスルホキシドを溶媒として行った。Add 270 g of imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 400 ml of chloroform (manufactured by Kanto Chemical Co., Ltd.), 188 g of 2-methoxyethyl chloride (manufactured by Kanto Chemical Co., Ltd.) to the autoclave in this order, and dissolve by stirring at 300 rpm. Then, the reaction was carried out at 90 ° C. and 250 rpm for 14 hours. At this time, the internal pressure was 0.12 kgf / cm 2 (0.012 MPa).
Chloroform was distilled off from the reaction solution with an evaporator, and a fraction having a boiling point of about 100 ° C. at 3 mmHg / cm 2 was collected by vacuum distillation. Since this fraction was a mixture of N-2-methoxyethylimidazole and imidazole, a part of the fraction was taken and purified by silica gel chromatography (chloroform: methanol = 50: 1). 35 g of imidazole was obtained. The structure was confirmed by 1 H-NMR.
Thereafter, compound (12) was prepared in substantially the same manner as in Synthesis Example 1 except that 2-methoxyethyldiethylamine was changed to N-2-methoxyethylimidazole obtained above and trimethylphosphoric acid was changed to dimethylphosphorous acid. Was synthesized. The compound was liquid at room temperature.
1 H-NMR spectrum of compound (12) (1-methoxyethyl-3-methylimidazolium methyl phosphite: [MEMIm] [(MeO) (H) PO 2 ]) obtained in Synthesis Example 7 7 shows. The measurement was performed using heavy dimethyl sulfoxide as a solvent.
［２］セルロースの溶解
［実施例１］
合成例１で得られたＮ，Ｎ−ジエチル−Ｎ−メチル−Ｎ−２−メトキシエチルアンモニウム ジメチルリン酸塩（［ＤＥＭＥ］［（ＭｅＯ）2ＰＯ2］）を、攪拌子を入れた２０ｍｌサンプル瓶に２ｇ分取し、１質量％量のセルロース（Ａｌｄｒｉｃｈ社製、微結晶セルロース（Micro Crystalline Cellulose）、分子量＝重合度２００〜３００）と混合した。
この混合物を乾燥機（Ｙａｍａｔｏ ＣＯＮＳＴＡＮＴ ＴＥＭＰＥＲＡＴＵＲＥ ＯＶＥＮ ＤＮ−４２）内に投入し、２５℃で３０分間保持した。この際、時々、サンプル瓶を取り出しては、スターラ（ＩＷＡＫＩ ＨＩＧＨ−ＰＯＷＥＲ ＳＴＩＲＲＥＲ ＢＳ−１０００）で攪拌した。イオン液体に添加したセルロースが溶解したことは、目視により、セルロースが分散混合した状態から均一透明な溶液になることで判断した。
また、３０分間でセルロースが溶解しなかった場合は５℃刻みで昇温し、３０分間でセルロースが溶解した場合は１質量％刻みで、セルロース量を増加させた。この操作を１００℃まで繰り返し、セルロースの溶解量と温度を記録した。[2] Dissolution of cellulose [Example 1]
A 20 ml sample containing a stirring bar of N, N-diethyl-N-methyl-N-2-methoxyethylammonium dimethyl phosphate ([DEME] [(MeO) 2 PO 2 ]) obtained in Synthesis Example 1 2 g was collected in a bottle and mixed with 1% by mass of cellulose (manufactured by Aldrich, Micro Crystalline Cellulose, molecular weight = degree of polymerization 200-300).
This mixture was put into a drier (Yamato CONSTANT TEMPERATURE OPEN DN-42) and held at 25 ° C. for 30 minutes. At this time, the sample bottle was taken out from time to time and stirred with a stirrer (IWAKI HIGH-POWER STIRRE BS-1000). The dissolution of the cellulose added to the ionic liquid was judged by visual observation from a state in which the cellulose was dispersed and mixed into a uniform transparent solution.
Moreover, when the cellulose did not melt | dissolve in 30 minutes, it heated up in steps of 5 degreeC, and when the cellulose melt | dissolved in 30 minutes, the amount of cellulose was increased in 1 mass% increments. This operation was repeated up to 100 ° C., and the amount of cellulose dissolved and the temperature were recorded.
［実施例２］
［ＤＥＭＥ］［（ＭｅＯ）2ＰＯ2］を合成例２で得られたＮ−メチル−Ｎ−２−メトキシエチルピロリジニウム ジメチルリン酸塩（［ＭＥＭＰ］［（ＭｅＯ）2ＰＯ2］）に変更した以外は、実施例１と同様に行った。[Example 2]
[DEME] [(MeO) 2 PO 2 ] to N-methyl-N-2-methoxyethylpyrrolidinium dimethyl phosphate ([MEMP] [(MeO) 2 PO 2 ]) obtained in Synthesis Example 2. The procedure was the same as in Example 1 except for the change.
［実施例３］
［ＤＥＭＥ］［（ＭｅＯ）2ＰＯ2］を合成例３で得られたＮ，Ｎ−ジエチル−Ｎ−メチル−Ｎ−２−メトキシエチルアンモニウム メチルジメチルホスホン酸塩（［ＤＥＭＥ］［（ＭｅＯ）（Ｍｅ）ＰＯ2］）に変更した以外は、実施例１と同様に行った。[Example 3]
[DEME] [(MeO) 2 PO 2 ] was synthesized from N, N-diethyl-N-methyl-N-2-methoxyethylammonium methyldimethylphosphonate ([DEME] [(MeO) ( Me) Performed in the same manner as in Example 1 except that it was changed to PO 2 ]).
［実施例４］
［ＤＥＭＥ］［（ＭｅＯ）2ＰＯ2］を合成例４で得られたＮ−メチル−Ｎ−２−メトキシエチルピロリジニウム メチルジメチルホスホン酸塩（［ＭＥＭＰ］［（ＭｅＯ）（Ｍｅ）ＰＯ2］）に変更した以外は、実施例１と同様に行った。[Example 4]
[DEME] [(MeO) 2 PO 2 ] was obtained by synthesizing N-methyl-N-2-methoxyethylpyrrolidinium methyldimethylphosphonate ([MEMP] [(MeO) (Me) PO 2 ) obtained in Synthesis Example 4. ]) The procedure was the same as Example 1 except that the change was made.
［実施例５］
［ＤＥＭＥ］［（ＭｅＯ）2ＰＯ2］を合成例５で得られたＮ，Ｎ−ジエチル−Ｎ−メチル−Ｎ−２−メトキシエチルアンモニウム メチル亜リン酸塩（［ＤＥＭＥ］［（ＭｅＯ）（Ｈ）ＰＯ2］）に変更した以外は、実施例１と同様に行った。[Example 5]
[DEME] [(MeO) 2 PO 2 ] was converted to N, N-diethyl-N-methyl-N-2-methoxyethylammonium methyl phosphite ([DEME] [(MeO) ( H) Performed in the same manner as in Example 1 except that it was changed to PO 2 ]).
［実施例６］
［ＤＥＭＥ］［（ＭｅＯ）2ＰＯ2］を合成例６で得られたＮ−メチル−Ｎ−２−メトキシエチルピロリジニウム メチル亜リン酸塩（［ＭＥＭＰ］［（ＭｅＯ）（Ｈ）ＰＯ2］）に変更した以外は、実施例１と同様に行った。[Example 6]
[DEME] [(MeO) 2 PO 2 ] was converted to N-methyl-N-2-methoxyethylpyrrolidinium methyl phosphite ([MEMP] [(MeO) (H) PO 2 ] obtained in Synthesis Example 6. ]) The procedure was the same as Example 1 except that the change was made.
［実施例７］
［ＤＥＭＥ］［（ＭｅＯ）2ＰＯ2］を合成例７で得られた１−メトキシエチル−３−メチルイミダゾリウム メチル亜リン酸塩（［ＭＥＭＩｍ］［（ＭｅＯ）（Ｈ）ＰＯ2］）に変更した以外は、実施例１と同様に行った。
上記実施例１〜７におけるセルロースの溶解量と温度を記録したグラフを図８に示す。[Example 7]
[DEME] [(MeO) 2 PO 2 ] into 1-methoxyethyl-3-methylimidazolium methyl phosphite ([MEMIm] [(MeO) (H) PO 2 ]) obtained in Synthesis Example 7. The procedure was the same as in Example 1 except for the change.
The graph which recorded the dissolution amount and temperature of the cellulose in the said Examples 1-7 is shown in FIG.
［実施例８］
合成例５で得られたＮ，Ｎ−ジエチル−Ｎ−メチル−Ｎ−２−メトキシエチルアンモニウム メチル亜リン酸塩（［ＤＥＭＥ］［（ＭｅＯ）（Ｈ）ＰＯ2］）を、攪拌子を入れた５ｍｌサンプル瓶に５００ｍｇ分取し、１質量％量のセルロース（Ａｌｄｒｉｃｈ社製、微結晶セルロース（Micro Crystalline Cellulose）、分子量＝重合度２００〜３００）と混合した。
この混合物を室温（２５℃）で１５時間攪拌し、イオン液体に添加したセルロースが溶解することを、目視により確認した。溶解したことはセルロースが分散混合した状態から均一透明な溶液になることで判断した。また、１５時間以内にセルロースが溶解した場合は、さらに１質量％刻みでセルロース量を増加させ、１５時間以内での溶解性を調査した。この操作を繰り返し、室温（２５℃）でのセルロースの溶解量を調査した。その結果、室温（２５℃）でのセルロースの溶解量は１質量％であった。[Example 8]
The N, N-diethyl-N-methyl-N-2-methoxyethylammonium methyl phosphite ([DEME] [(MeO) (H) PO 2 ]) obtained in Synthesis Example 5 was placed in a stir bar. Further, 500 mg was taken into a 5 ml sample bottle and mixed with 1% by mass of cellulose (manufactured by Aldrich, Micro Crystalline Cellulose, molecular weight = degree of polymerization 200 to 300).
This mixture was stirred at room temperature (25 ° C.) for 15 hours, and it was visually confirmed that the cellulose added to the ionic liquid was dissolved. The dissolution was judged by a uniform transparent solution from the state where cellulose was dispersed and mixed. When the cellulose was dissolved within 15 hours, the amount of cellulose was further increased in increments of 1% by mass, and the solubility within 15 hours was investigated. This operation was repeated to investigate the amount of cellulose dissolved at room temperature (25 ° C.). As a result, the dissolution amount of cellulose at room temperature (25 ° C.) was 1% by mass.
［実施例９］
［ＤＥＭＥ］［（ＭｅＯ）（Ｈ）ＰＯ2］を合成例６で得られたＮ−メチル−Ｎ−２−メトキシエチルピロリジニウム メチル亜リン酸塩（［ＭＥＭＰ］［（ＭｅＯ）（Ｈ）ＰＯ2］）に変更した以外は、実施例８と同様に行った。その結果、室温（２５℃）でのセルロースの溶解量は１質量％であった。[Example 9]
[DEME] [(MeO) (H) PO 2 ] was converted to N-methyl-N-2-methoxyethylpyrrolidinium methyl phosphite ([MEMP] [(MeO) (H)) obtained in Synthesis Example 6. The same procedure as in Example 8 was performed except that PO 2 ]) was changed. As a result, the dissolution amount of cellulose at room temperature (25 ° C.) was 1% by mass.
［実施例１０］
［ＤＥＭＥ］［（ＭｅＯ）（Ｈ）ＰＯ2］を合成例７で得られた１−メトキシエチル−３−メチルイミダゾリウム メチル亜リン酸塩（［ＭＥＭＩｍ］［（ＭｅＯ）（Ｈ）ＰＯ2］）に変更した以外は、実施例８と同様に行った。その結果、室温（２５℃）でのセルロースの溶解量は５質量％であった。[Example 10]
[DEME] [(MeO) (H) PO 2 ] was converted to 1-methoxyethyl-3-methylimidazolium methyl phosphite obtained in Synthesis Example 7 ([MEMIm] [(MeO) (H) PO 2 ]). The procedure was the same as in Example 8 except that the change was made to). As a result, the dissolution amount of cellulose at room temperature (25 ° C.) was 5% by mass.
［３］セルロースの再生
［実施例１１］
実施例９と同様にして、セルロースを、［ＭＥＭＰ］［（ＭｅＯ）（Ｈ）ＰＯ2］に溶かし、セルロースの［ＭＥＭＰ］［（ＭｅＯ）（Ｈ）ＰＯ2］溶液（含有セルロース：１質量％）を調製した。この溶液５００ｍｇを、攪拌下で水５ｇに少しずつに分けて加え、最終的に全量加えた後、１０分間攪拌を続けてセルロースを析出させた。
デカンテーションにより水相を捨て、新たに５ｇの水を加えて攪拌する操作を４回繰り返してセルロースから［ＭＥＭＰ］［（ＭｅＯ）（Ｈ）ＰＯ2］を洗い流し、塊状のセルロースを得た。乾燥後の塊状セルロースの質量は４．９ｍｇであった。[3] Regeneration of cellulose [Example 11]
In the same manner as in Example 9, cellulose was dissolved in [MEMP] [(MeO) (H) PO 2 ], and a [MEMP] [(MeO) (H) PO 2 ] solution of cellulose (containing cellulose: 1% by mass) ) Was prepared. 500 mg of this solution was added in portions to 5 g of water under stirring, and finally the whole amount was added, followed by stirring for 10 minutes to precipitate cellulose.
The aqueous phase was discarded by decantation, and an operation of adding 5 g of water and stirring the mixture was repeated four times to wash out [MEMP] [(MeO) (H) PO 2 ] from the cellulose to obtain bulky cellulose. The mass of the bulk cellulose after drying was 4.9 mg.
Claims (12)
Ｒ1Ｒ2Ｒ3Ｒ4Ｎ+ ・・・（１）
〔式中、Ｒ1、Ｒ2、Ｒ3およびＲ4は、互いに同一でも異なっていてもよい、炭素数１〜１２の直鎖もしくは分岐のアルキル基、または−（ＣＨ2）n−ＯＲ5で示されるアルコキシアルキル基（Ｒ5は、メチル基またはエチル基を示し、ｎは、１または２である。）を示し（ただし、Ｒ1、Ｒ2、Ｒ3およびＲ4の少なくとも１つは前記アルコキシアルキル基である。）、これらＲ1、Ｒ2、Ｒ3およびＲ4のいずれか２個の基が窒素原子とともに環（当該環中にその他のヘテロ原子を含んでいてもよい。）を形成していてもよい。〕 An ionic liquid comprising a quaternary ammonium cation represented by the formula (1) and (CH 3 O) (R) PO 2 − (R represents a hydrogen atom, a methyl group or a methoxy group).
R 1 R 2 R 3 R 4 N + (1)
[Wherein R 1 , R 2 , R 3 and R 4 may be the same as or different from each other, a linear or branched alkyl group having 1 to 12 carbon atoms, or — (CH 2 ) n —OR 5. (Wherein R 5 represents a methyl group or an ethyl group, and n is 1 or 2), provided that at least one of R 1 , R 2 , R 3 and R 4 is Any one of R 1 , R 2 , R 3 and R 4 together with a nitrogen atom in a ring (other heteroatoms may be contained in the ring). May be formed. ]
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| US9777074B2 (en) | 2008-02-13 | 2017-10-03 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom |
| US8158777B2 (en) | 2008-02-13 | 2012-04-17 | Eastman Chemical Company | Cellulose esters and their production in halogenated ionic liquids |
| US8354525B2 (en) | 2008-02-13 | 2013-01-15 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom |
| US8524887B2 (en) * | 2009-04-15 | 2013-09-03 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a tetraalkylammonium alkylphosphate ionic liquid process and products produced therefrom |
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| JP5624820B2 (en) * | 2010-07-12 | 2014-11-12 | 株式会社ブリヂストン | Method for producing purified cellulose fiber |
| JP5578015B2 (en) * | 2010-10-19 | 2014-08-27 | Ｊｓｒ株式会社 | Method for producing cellulose particles, and cellulose particles |
| JP5874993B2 (en) * | 2010-10-20 | 2016-03-02 | 国立大学法人金沢大学 | Biotreatment method for biomass |
| WO2012081616A1 (en) * | 2010-12-14 | 2012-06-21 | Jsr株式会社 | Method for producing polymer particles, and polymer particles |
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| JP2022129896A (en) * | 2021-02-25 | 2022-09-06 | ミヨシ油脂株式会社 | Organic ammonium salt having phosphonate or phosphinate anion, and composition capable of forming the salt |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2486079A1 (en) * | 1980-07-07 | 1982-01-08 | Rhone Poulenc Agrochimie | 1,3-Alkyl or benzyl substd. imidazolium phosphite derivs. - are fungicides active against basidiomycetes, ascomycetes, phycomycetes and fungi imperfecti |
| JP2002003478A (en) * | 2000-06-20 | 2002-01-09 | Japan Science & Technology Corp | N-alkoxyalkyl imidazolium salt and ionic liquid and ionic gel composed of the imidazolium salt |
| WO2004016631A1 (en) * | 2002-08-16 | 2004-02-26 | Cytec Canada Inc. | Phosphonium and imidazolium salts and methods of their preparation |
| JP2005506401A (en) * | 2001-10-03 | 2005-03-03 | ザ ユニヴァーシティー オブ アラバマ | Dissolution and processing of cellulose using ionic liquids |
| JP2005530910A (en) * | 2002-06-28 | 2005-10-13 | ザ プロクター アンド ギャンブル カンパニー | Ionic liquid products and methods of use |
| WO2007049485A1 (en) * | 2005-10-25 | 2007-05-03 | Nisshinbo Industries, Inc. | Process for producing cellulose solution, cellulose solution, and process for producing regenerated cellulose |
| JP2009520846A (en) * | 2005-12-23 | 2009-05-28 | ビーエーエスエフ ソシエタス・ヨーロピア | Solvent system based on molten ionic liquid, its production and its use to produce regenerated carbohydrates |
-
2008
- 2008-04-23 JP JP2009511883A patent/JP5339452B2/en active Active
- 2008-04-23 WO PCT/JP2008/057836 patent/WO2008133269A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2486079A1 (en) * | 1980-07-07 | 1982-01-08 | Rhone Poulenc Agrochimie | 1,3-Alkyl or benzyl substd. imidazolium phosphite derivs. - are fungicides active against basidiomycetes, ascomycetes, phycomycetes and fungi imperfecti |
| JP2002003478A (en) * | 2000-06-20 | 2002-01-09 | Japan Science & Technology Corp | N-alkoxyalkyl imidazolium salt and ionic liquid and ionic gel composed of the imidazolium salt |
| JP2005506401A (en) * | 2001-10-03 | 2005-03-03 | ザ ユニヴァーシティー オブ アラバマ | Dissolution and processing of cellulose using ionic liquids |
| JP2005530910A (en) * | 2002-06-28 | 2005-10-13 | ザ プロクター アンド ギャンブル カンパニー | Ionic liquid products and methods of use |
| WO2004016631A1 (en) * | 2002-08-16 | 2004-02-26 | Cytec Canada Inc. | Phosphonium and imidazolium salts and methods of their preparation |
| WO2007049485A1 (en) * | 2005-10-25 | 2007-05-03 | Nisshinbo Industries, Inc. | Process for producing cellulose solution, cellulose solution, and process for producing regenerated cellulose |
| JP2009520846A (en) * | 2005-12-23 | 2009-05-28 | ビーエーエスエフ ソシエタス・ヨーロピア | Solvent system based on molten ionic liquid, its production and its use to produce regenerated carbohydrates |
Non-Patent Citations (1)
| Title |
|---|
| JPN6013022877; Ｇｒｅｅｎ Ｃｈｅｍｉｓｔｒｙ Ｖｏｌ． ９, 2006, Ｐ． ２３３-２４２ * |
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