JP2015020954A - Method for synthesizing ammonium salt and composition obtained by incorporating polysaccharides into ammonium salt - Google Patents
Method for synthesizing ammonium salt and composition obtained by incorporating polysaccharides into ammonium salt Download PDFInfo
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- 150000003863 ammonium salts Chemical class 0.000 title claims abstract description 28
- 150000004676 glycans Chemical class 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 229920001282 polysaccharide Polymers 0.000 title claims abstract description 26
- 239000005017 polysaccharide Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- 229920002101 Chitin Polymers 0.000 claims abstract description 25
- 229920002678 cellulose Polymers 0.000 claims abstract description 20
- 239000001913 cellulose Substances 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims description 20
- 150000001412 amines Chemical class 0.000 claims description 13
- 229920001661 Chitosan Polymers 0.000 claims description 12
- GNPSDJOWGWWXSS-UHFFFAOYSA-M 1-benzylpyridin-1-ium;chloride Chemical compound [Cl-].C=1C=CC=C[N+]=1CC1=CC=CC=C1 GNPSDJOWGWWXSS-UHFFFAOYSA-M 0.000 claims description 11
- 238000001308 synthesis method Methods 0.000 claims description 11
- -1 benzyl halide Chemical class 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 230000000007 visual effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- HHRGJJOAJXTPJT-UHFFFAOYSA-N C(C1=CC=CC=C1)Cl.Cl.C(C1=CC=CC=C1)N1CCCC1 Chemical compound C(C1=CC=CC=C1)Cl.Cl.C(C1=CC=CC=C1)N1CCCC1 HHRGJJOAJXTPJT-UHFFFAOYSA-N 0.000 description 1
- AQZLIWQCRISWTB-UHFFFAOYSA-M C(C1=CC=CC=C1)Cl.[Cl-].C(C)[N+](C1=CC=CC=C1)(CC)CC Chemical compound C(C1=CC=CC=C1)Cl.[Cl-].C(C)[N+](C1=CC=CC=C1)(CC)CC AQZLIWQCRISWTB-UHFFFAOYSA-M 0.000 description 1
- WUJPJPROKUBLDF-UHFFFAOYSA-M C(C1=CC=CC=C1)Cl.[Cl-].C(C1=CC=CC=C1)[N+]1=CC=C(C=C1)N(C)C Chemical compound C(C1=CC=CC=C1)Cl.[Cl-].C(C1=CC=CC=C1)[N+]1=CC=C(C=C1)N(C)C WUJPJPROKUBLDF-UHFFFAOYSA-M 0.000 description 1
- MVOQPSAHDVQEMB-UHFFFAOYSA-M C(C1=CC=CC=C1)Cl.[Cl-].C(C1=CC=CC=C1)[N+]1=CC=CC=C1 Chemical compound C(C1=CC=CC=C1)Cl.[Cl-].C(C1=CC=CC=C1)[N+]1=CC=CC=C1 MVOQPSAHDVQEMB-UHFFFAOYSA-M 0.000 description 1
- JQAJUJBEJYDQQA-UHFFFAOYSA-N C(C1=CC=CC=C1)Cl.[Cl-].C(C1=CC=CC=C1)[N+]1=CNC=C1 Chemical compound C(C1=CC=CC=C1)Cl.[Cl-].C(C1=CC=CC=C1)[N+]1=CNC=C1 JQAJUJBEJYDQQA-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Pyridine Compounds (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
この発明は、アンモニウム塩の短時間製造法およびアンモニウム塩とセルロース、キチン等の多糖類を含有した新たな組成物に関する。 The present invention relates to a short-time production method of an ammonium salt and a new composition containing an ammonium salt and a polysaccharide such as cellulose and chitin.
第四級アンモニウム塩の合成方法として、アルコールに水を混ぜ行っていることが報告されている。（特許文献１） It has been reported that alcohol is mixed with water as a method for synthesizing a quaternary ammonium salt. (Patent Document 1)
加熱を行うと沸点の低いものが先に蒸発し、いわゆる還流状態となることが知られている。還流を行う場合は、蒸気が冷却管の下部の端で凝結するのが見える程度の加熱がよいとされている。加熱のしすぎは、冷却トラップの能力を超えることによる蒸発乾固の危険性や、引火点や発火点の関係もあり、好ましくないとされている。なお、還流条件での反応温度は、反応溶媒の沸点付近となることが知られている。（非特許文献１） It is known that when heating is performed, those having a low boiling point evaporate first, and a so-called reflux state is obtained. When refluxing is performed, it is said that heating is good enough to allow vapor to condense at the lower end of the cooling pipe. Excessive heating is considered to be unfavorable due to the risk of evaporation to dryness exceeding the capacity of the cooling trap and the relationship between the flash point and ignition point. It is known that the reaction temperature under reflux conditions is around the boiling point of the reaction solvent. (Non-Patent Document 1)
年間生産量１兆トンともいわれている、多くの生物に含まれているセルロース、キチン、キトサンなどの多糖類は、その利用に大きな関心が寄せられている。しかしながら、セルロース、キチン、キトサンなどは、その分子内に存在する強固な分子内水素結合によって、溶媒への溶解性が悪いことが知られており、その利活用が進まない大きな要因となっている。 Polysaccharides such as cellulose, chitin, and chitosan contained in many organisms, which are said to have an annual production of 1 trillion tons, are attracting great interest in their use. However, cellulose, chitin, chitosan, etc. are known to have poor solubility in solvents due to the strong intramolecular hydrogen bonds present in the molecule, and this is a major factor that prevents their utilization. .
第四級アンモニウム塩と呼ばれる、分子内にカチオンやアニオンを有する化合物が、セルロースなど多糖類を溶解することが報告されている。しかしながら、塩素を含む第四級アンモニウム塩では、セルロースを溶解しても、キチンを溶解するにはいたっていない。（例えば、特許文献２、特許文献３参照。） It has been reported that a compound called a quaternary ammonium salt having a cation or an anion in the molecule dissolves polysaccharides such as cellulose. However, with quaternary ammonium salts containing chlorine, even when cellulose is dissolved, chitin is not dissolved. (For example, see Patent Document 2 and Patent Document 3.)
特許文献１には、第四級アンモニウム塩の合成法について、アルコールに水を混ぜ、７０度で３．３時間かかることが記載されている。また、特許文献２等では、セルロースやキチン等の多糖類を、イミダゾール骨格を基にした第四級アンモニウム塩で溶解させることが記載されている。しかしながら、塩素を含む第四級アンモニウム塩では、セルロースを溶解しても、キチンを溶解するにはいたっていない。
本発明は、第四級アンモニウム塩を含むアンモニウム塩をこれまで知られた例より短時間で作る合成法を提供すること、アンモニウム塩とセルロースやキチン等の多糖類を含有した新たな組成物を提供することを目的とする。
Patent Document 1 describes that a method for synthesizing a quaternary ammonium salt takes 3.3 hours at 70 ° C. by mixing water with alcohol. Patent Document 2 and the like describe dissolving polysaccharides such as cellulose and chitin with a quaternary ammonium salt based on an imidazole skeleton. However, with quaternary ammonium salts containing chlorine, even when cellulose is dissolved, chitin is not dissolved.
The present invention provides a synthesis method for producing an ammonium salt containing a quaternary ammonium salt in a shorter time than previously known examples, and a new composition containing an ammonium salt and a polysaccharide such as cellulose or chitin. The purpose is to provide.
請求項１に係る発明は、アミンとベンジルハライドを１２０℃以上で加熱反応させるアンモニウム塩の合成方法であることを特徴とする。 The invention according to claim 1 is a method for synthesizing an ammonium salt in which an amine and benzyl halide are heated and reacted at 120 ° C. or higher.
請求項２に係る発明は、前記のアミンが、下記一般式（化１）、（化２）、（化３）、（化４）で表される化合物の少なくとも１種を含む請求項１に記載の合成方法であることを特徴とする。
請求項３に係る発明は、前記のベンジルハライドが、下記一般式（化５）で表される化合物である請求項１又は２に記載の合成方法であることを特徴とする。
（式中、Xは独立にハロゲンを意味する。）
The invention according to claim 3 is the synthesis method according to claim 1 or 2, wherein the benzyl halide is a compound represented by the following general formula (Formula 5).
(In the formula, X independently represents halogen.)
請求項４に係る発明は、請求項１〜３のいずれかに記載の合成方法により得られた１−ベンジルピリジニウムクロライドに多糖類を溶解して含有する組成物であることを特徴とする。 The invention according to claim 4 is a composition containing a polysaccharide dissolved in 1-benzylpyridinium chloride obtained by the synthesis method according to any one of claims 1 to 3.
請求項５に係る発明は、前記多糖類が、セルロース、キチン、キトサンの少なくとも１種を含む請求項４に記載の組成物であることを特徴とする。 The invention according to claim 5 is the composition according to claim 4, wherein the polysaccharide contains at least one of cellulose, chitin, and chitosan.
請求項６に係る発明は、請求項１〜３のいずれかに記載の合成法により得られた１−ベンジルピリジニウムクロライドに多糖類を添加し、そのまま加熱またはアルコールを添加し加熱することで、多糖類を溶解させる多糖類の含有組成物の製造方法であることを特徴とする。 The invention according to claim 6 is obtained by adding a polysaccharide to 1-benzylpyridinium chloride obtained by the synthesis method according to any one of claims 1 to 3, and heating it as it is or adding alcohol and heating. It is a method for producing a polysaccharide-containing composition in which saccharides are dissolved.
請求項７に係る発明は、前記多糖類が、セルロース、キチン、キトサンの少なくとも１種を含む請求項６に記載の製造方法であることを特徴とする。 The invention according to claim 7 is the production method according to claim 6, wherein the polysaccharide contains at least one of cellulose, chitin, and chitosan.
請求項１、請求項２、請求項３に係る発明によると、第四級アンモニウム塩を含むアンモニウム塩をこれまで報告されている合成方法に比べて、２０〜２００分の１の時間、同じ転化率で合成することができる。 According to the inventions according to claim 1, claim 2, and claim 3, ammonium salt containing quaternary ammonium salt is converted in the same amount of time for 20 to 1/200 times as compared with the synthesis methods reported so far. Can be synthesized at a rate.
請求項４、請求項５、請求項６、請求項７に係る発明によると、１−ベンジルピリジニウムクロライドにセルロース、キチン、キトサンを少なくとも１種を含む組成物を加熱することで提供することができる。 According to the invention which concerns on Claim 4, Claim 5, Claim 6, Claim 7, it can provide by heating the composition which contains cellulose, chitin, and chitosan at least 1 sort (s) in 1-benzyl pyridinium chloride. .
本発明のアンモニウム塩の合成法において、原料となるアミンとハロゲン化物は特に限定されないが、例えば、（化６）から（化１５）に示す化学式で示される骨格をもったものを使用するのが好ましい。
また、原料となるアミンとハロゲン化物のモル比（アミン：ハロゲン化物）は、特に限定されないが、通常１〜６５０：１、好ましくは１：１である。 The molar ratio of amine and halide (amine: halide) as a raw material is not particularly limited, but is usually 1 to 650: 1, preferably 1: 1.
反応を行う際に使う溶媒はアミンとハロゲン化物を溶解できれば、特に限定されないが、通常はアミン、アルコール、エーテルやアセトニトリルなど、好ましくは溶媒を使用しないことである。 The solvent used in the reaction is not particularly limited as long as it can dissolve the amine and the halide. Usually, an amine, alcohol, ether, acetonitrile, or the like is preferably used without using a solvent.
反応温度については、アミンの種類により異なり、反応温度を高くすれば反応時間を短くすることができるため、特に限定されないが、通常１２０℃以上、好ましくは１２０℃〜１５０℃である。 The reaction temperature varies depending on the type of amine, and the reaction time can be shortened by increasing the reaction temperature. Therefore, the reaction temperature is not particularly limited, but is usually 120 ° C or higher, preferably 120 ° C to 150 ° C.
製造方法の１例を示すと、まず、アミンとベンジルハライド誘導体を等モル量ずつ加え、通常１２０℃以上で１〜１０分加熱して、目的とするアンモニウム塩を合成する。 As an example of the production method, an amine and a benzyl halide derivative are first added in equimolar amounts, and usually heated at 120 ° C. or higher for 1 to 10 minutes to synthesize a target ammonium salt.
上記記載のアンモニウム塩と多糖類としてセルロース、キチン、キトサンを含有した組成物の製造方法において、原料となる多糖類、例えばキチンとアンモニウム塩との重量比（キチン：アンモニウム塩）は、通常０．０１〜０．０７：１、好ましくは０．０２〜０．０５：１である。 In the above method for producing a composition containing cellulose, chitin, and chitosan as a polysaccharide, the weight ratio of the raw material polysaccharide, for example, chitin and ammonium salt (chitin: ammonium salt) is usually 0.00. 01 to 0.07: 1, preferably 0.02 to 0.05: 1.
溶媒については、アンモニウム塩を溶解できれば、特に限定されないが、通常はアミン、アルコール、エーテルやアセトニトリルなど、好ましくは溶媒を使用しないことである。 The solvent is not particularly limited as long as the ammonium salt can be dissolved, but usually a solvent such as amine, alcohol, ether or acetonitrile is preferably used.
製造方法の１例を示すと、まずアンモニウム塩にキチンを加え、通常１４０℃〜１６０℃の温度で１時間〜１２時間混合物を加熱して、キチンをアンモニウム塩に完全に溶解させる。その後、室温まで冷却し目的とする組成物を得ることができる。 As an example of the production method, chitin is first added to an ammonium salt, and the mixture is usually heated at a temperature of 140 ° C. to 160 ° C. for 1 to 12 hours to completely dissolve the chitin in the ammonium salt. Then, it cools to room temperature and can obtain the target composition.
得られた組成物に、アンモニウム塩に溶解するが多糖類を溶解しない溶剤を加えることで、原料である多糖類を全量回収することができる。適した溶剤は用いるアンモニウム塩により異なるが、例えば、アンモニウム塩が１−ベンジルピリジニウムクロライドであり、多糖類がキチンの場合、溶剤にアセトニトリルを加えることで、原料である多糖類を回収することができる。 By adding a solvent that dissolves in the ammonium salt but does not dissolve the polysaccharide, the total amount of the polysaccharide as a raw material can be recovered. A suitable solvent varies depending on the ammonium salt used. For example, when the ammonium salt is 1-benzylpyridinium chloride and the polysaccharide is chitin, the raw material polysaccharide can be recovered by adding acetonitrile to the solvent. .
実施例におけるアンモニウム塩の構造確認は、１H−NMR（nanalysis社製）を用いて行った。また、アンモニウム塩に加えたセルロース、キチン、キトサンが溶解したことは、目視により、均一透明な溶液になることで判断した。 The structure of the ammonium salt in Examples was confirmed using 1H-NMR (manufactured by nanalysis). Moreover, it was judged by visual observation that the cellulose, chitin, and chitosan added to the ammonium salt were dissolved to form a uniform transparent solution.
［実施例１］
１−ベンジルピリジニウムクロライド
ベンジルクロライド（和光純薬工業（株）製）５．４４ｇ（４３ｍｍｏｌ）とピリジン（和光純薬工業（株）製）３．４０ｇ（４３ｍｍｏｌ）を室温で撹拌混合し、１４５℃〜１５０℃で５分加熱した。加熱を行うと沸点１１５℃のピリジンによる還流が始まるが、すぐに溶液がワインレッドに変化し、沸騰が収まる。室温まで冷却して目的のものを得た。
[Example 1]
1-Benzylpyridinium chloride Benzyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) 5.44 g (43 mmol) and pyridine (manufactured by Wako Pure Chemical Industries, Ltd.) 3.40 g (43 mmol) were stirred and mixed at room temperature. Heated at ˜150 ° C. for 5 minutes. When heated, refluxing with pyridine having a boiling point of 115 ° C. starts, but immediately the solution changes to wine red and the boiling stops. The desired product was obtained after cooling to room temperature.
［実施例２］
１−ベンジル−４−（ジメチルアミノ）ピリジニウムクロライド
ベンジルクロライド（和光純薬工業（株）製）５．４４ｇ（４３ｍｍｏｌ）と４−ジメチルアミノピリジン（和光純薬工業（株）製）５．２５ｇ（４３ｍｍｏｌ）を室温で撹拌混合し、１２５℃で５分加熱した。湯浴温度が上がるにつれて液体が急速に固体に変化し、得られた白い固体をメタノールに溶かし、ろ過した後、濃縮し、目的のものを得た。
[Example 2]
5-44 g (43 mmol) of 1-benzyl-4- (dimethylamino) pyridinium chloride benzyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 5.25 g of 4-dimethylaminopyridine (manufactured by Wako Pure Chemical Industries, Ltd.) 43 mmol) was stirred and mixed at room temperature and heated at 125 ° C. for 5 minutes. The liquid rapidly changed to a solid as the bath temperature increased, and the resulting white solid was dissolved in methanol, filtered and concentrated to obtain the desired product.
［実施例３］
N,N,N-トリエチルベンゼンアミニウムクロライド
ベンジルクロライド（和光純薬工業（株）製）５．１９ｇ（４１ｍｍｏｌ）とトリエチルアミン（和光純薬工業（株）製）４．１５ｇ（４１ｍｍｏｌ）を室温で撹拌混合し、１２０℃で５分加熱した。得られた白い固体をメタノールに溶かし、ろ過した後、濃縮し、目的のものを得た。
[Example 3]
5.19 g (41 mmol) of N, N, N-triethylbenzeneaminium chloride benzyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 4.15 g (41 mmol) of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) at room temperature The mixture was stirred and heated at 120 ° C. for 5 minutes. The obtained white solid was dissolved in methanol, filtered, and concentrated to obtain the desired product.
［実施例４］
１−ベンジルピロリジンハイドロクロライド
ベンジルクロライド（和光純薬工業（株）製）４．５６ｇ（３６ｍｍｏｌ）とピロリジン（和光純薬工業（株）製）２．５６ｇ（３６ｍｍｏｌ）を０℃で撹拌混合し、その後１２０℃で５分加熱し目的のものを得た。
[Example 4]
1-benzylpyrrolidine hydrochloride benzyl chloride (Wako Pure Chemical Industries, Ltd.) 4.56 g (36 mmol) and pyrrolidine (Wako Pure Chemical Industries, Ltd.) 2.56 g (36 mmol) were stirred and mixed at 0 ° C. Thereafter, the mixture was heated at 120 ° C. for 5 minutes to obtain the intended product.
［実施例５］
１−ベンジルイミダゾリウムクロライド
ベンジルクロライド（和光純薬工業（株）製）４．５６ｇ（３６ｍｍｏｌ）とイミダゾール（和光純薬工業（株）製）２．５６ｇ（３６ｍｍｏｌ）を０℃で撹拌混合し、その後１２５℃で５分加熱し目的のものを得た。
[Example 5]
1-Benzylimidazolium chloride Benzyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) 4.56 g (36 mmol) and imidazole (manufactured by Wako Pure Chemical Industries, Ltd.) 2.56 g (36 mmol) were stirred and mixed at 0 ° C. Thereafter, the mixture was heated at 125 ° C. for 5 minutes to obtain the desired product.
［実施例６］
１−ベンジルピリジニウムクロライド８．８４ｇ（４３ｍｍｏｌ）に、キチン（和光純薬工業（株）製）０．５ｇを加え、１５５℃で２時間加熱した。溶解は、目視により透明になることで確認し、目的とする組成物を得た。
[Example 6]
0.5 g of chitin (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 8.84 g (43 mmol) of 1-benzylpyridinium chloride and heated at 155 ° C. for 2 hours. The dissolution was confirmed by visual observation and the intended composition was obtained.
［実施例７］
１−ベンジルピリジニウムクロライド８．８４ｇ（４３ｍｍｏｌ）に、キトサン（和光純薬工業（株）製）０．２ｇを加え、１５５℃で２時間加熱した。溶解は、目視により透明になることで確認し、目的とする組成物を得た。
[Example 7]
0.2 g of chitosan (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 8.84 g (43 mmol) of 1-benzylpyridinium chloride, and the mixture was heated at 155 ° C. for 2 hours. The dissolution was confirmed by visual observation and the intended composition was obtained.
［実施例８］
１−ベンジルピリジニウムクロライド８．８４ｇ（４３ｍｍｏｌ）に、５Cセルロースろ紙（ADVANTEC製）１．０ｇを加え、１５５℃で３０分加熱した。溶解は、目視により透明になることで確認し、目的とする組成物を得た。
[Example 8]
To 8.84 g (43 mmol) of 1-benzylpyridinium chloride, 1.0 g of 5C cellulose filter paper (manufactured by ADVANTEC) was added and heated at 155 ° C. for 30 minutes. The dissolution was confirmed by visual observation and the intended composition was obtained.
［実施例９］
１−ベンジルピリジニウムクロライド８．８４ｇ（４３ｍｍｏｌ）に、キチン０．１ｇ、キトサン０．１ｇ、５Cセルロースろ紙０．５ｇを加え、１５５℃で２時間加熱した。溶解は、目視により透明になることで確認し、目的とする組成物を得た。
[Example 9]
To 8.84 g (43 mmol) of 1-benzylpyridinium chloride, 0.1 g of chitin, 0.1 g of chitosan, and 0.5 g of 5C cellulose filter paper were added and heated at 155 ° C. for 2 hours. The dissolution was confirmed by visual observation and the intended composition was obtained.
［実施例１０］
１−ベンジルピリジニウムクロライド８．８４ｇ（４３ｍｍｏｌ）に、２．５５ｍｌのメタノールを加え撹拌した。次いでキチン０．１ｇを加え、冷却管を付け、１２５℃で１時間加熱した。溶解は、目視により透明になることで確認し、目的とする組成物を得た。
[Example 10]
To 8.84 g (43 mmol) of 1-benzylpyridinium chloride, 2.55 ml of methanol was added and stirred. Next, 0.1 g of chitin was added, a condenser tube was attached, and the mixture was heated at 125 ° C. for 1 hour. The dissolution was confirmed by visual observation and the intended composition was obtained.
この発明に係るアンモニウム塩の合成方法は、従来から知られている方法に比べ短時間かつ高効率で目的とするアンモニウム塩を作ることができる。また、溶媒を用いずに合成することも可能であるため、廃棄物のでない環境にやさしい合成方法といえる。
また、アミンであるピリジンとベンジルハライド誘導体を反応させて得られるアンモニウム塩、及びセルロース、キチン、キトサンを含む多糖類を少なくとも１種を含む組成物は、室温ではゲル状で、加熱すると流動性を持つため、加工性にすぐれ、繊維や薄膜形成などに用いられる。この発明は、化学工業一般への適用が可能である。
According to the method for synthesizing an ammonium salt according to the present invention, a target ammonium salt can be produced in a short time and with high efficiency as compared with a conventionally known method. Moreover, since it is also possible to synthesize without using a solvent, it can be said to be an environment-friendly synthesis method without waste.
In addition, a composition containing at least one ammonium salt obtained by reacting amine pyridine with a benzyl halide derivative and a polysaccharide containing cellulose, chitin, and chitosan is gel-like at room temperature. It has excellent processability and is used for forming fibers and thin films. The present invention can be applied to the chemical industry in general.
Claims (7)
（式中、Xは独立にハロゲンを意味する。） The synthesis method according to claim 1 or 2, wherein the benzyl halide is a compound represented by the following general formula (Formula 5).
(In the formula, X independently represents halogen.)
The said polysaccharide is a manufacturing method of Claim 6 containing at least 1 sort (s) of a cellulose, chitin, and chitosan.
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