JP2018090694A - Nano nitrocellulose and production method thereof - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000000020 Nitrocellulose Substances 0.000 title claims abstract description 19
- 229920001220 nitrocellulos Polymers 0.000 title claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000006396 nitration reaction Methods 0.000 claims abstract description 37
- 239000002253 acid Substances 0.000 claims abstract description 23
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 13
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 12
- 239000002360 explosive Substances 0.000 claims description 6
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- 230000018044 dehydration Effects 0.000 abstract description 8
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- 238000004108 freeze drying Methods 0.000 abstract description 6
- 235000011149 sulphuric acid Nutrition 0.000 abstract 2
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- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 abstract 1
- 208000005156 Dehydration Diseases 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 9
- 238000001523 electrospinning Methods 0.000 description 8
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- 238000009835 boiling Methods 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
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- 238000002156 mixing Methods 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- 238000011835 investigation Methods 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920002160 Celluloid Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
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Abstract
Description
本発明は、ナノニトロセルロース(以下「ｎ-ＮＣ」ということがある)及びその製造方法に関するものである。 The present invention relates to nanonitrocellulose (hereinafter sometimes referred to as “n-NC”) and a method for producing the same.
ニトロセルロース(以下「ＮＣ」ということがある)は、危険物第５類に指定され、無煙火薬(砲弾や銃器の発射薬)として使用されるほか、塗料、医薬、接着剤、セルロイド等の用途分野においても使用されている。 Nitrocellulose (hereinafter sometimes referred to as “NC”) is designated as a hazardous material class 5 and is used as smokeless gunpowder (a projectile for shells and firearms), as well as for paints, medicines, adhesives, celluloid, etc. It is also used in the field.
従来のＮＣは、セルロースとしての綿に硝酸と硫酸からなる混酸を反応させて製造するのが通常である。その際、セルロースを構成するグルコースは１単位分子当たり最大３カ所で硝酸エステル化(ニトロ化＝硝化)される。硝化反応は極めて速く、生成したＮＣは、洗浄して酸を除去した後、真空乾燥や空気乾燥により乾燥させる。硝化により製造されたＮＣは、窒素の含有量により、13％以上のものを強綿薬、10％未満のものを脆綿薬、それらの間のものを弱綿薬と称せられる。 Conventional NC is usually produced by reacting cotton as cellulose with a mixed acid composed of nitric acid and sulfuric acid. At this time, glucose constituting the cellulose is nitrated (nitrated = nitrified) at a maximum of three locations per unit molecule. The nitrification reaction is extremely fast, and the produced NC is washed to remove the acid and then dried by vacuum drying or air drying. NCs produced by nitrification are referred to as strong cotton drugs, those with less than 10% as brittle cotton drugs, and those between them as weak cotton drugs, depending on the nitrogen content.
微細なＮＣを得るための従来の研究としては、既存のＮＣを溶媒に溶かして、エレクトロスピニング法(電界紡糸法)により、径が90〜150, 400〜500nmなどのナノファイバー状のＮＣを製造したもの(非特許文献１参照)、有機溶媒に溶かしたＮＣをガラス基板上に滴下、乾燥してサブミクロンサイズ(直径200〜900nm)の粒子状ＮＣを製造したもの(非特許文献２参照)等が知られている。 Conventional research for obtaining fine NCs involves dissolving existing NCs in a solvent and producing nanofiber NCs with diameters of 90 to 150, 400 to 500 nm by electrospinning (electrospinning). (See Non-Patent Document 1), NC dissolved in an organic solvent is dropped on a glass substrate and dried to produce a sub-micron-sized (200 to 900 nm diameter) particulate NC (see Non-Patent Document 2) Etc. are known.
本発明者らは、従来のＮＣは、比表面積が大きくないため燃焼性能が十分でなく、煙火等に使用される割薬、打揚薬への応用展開が困難であること等の問題点が存在することを認識した。そして、従来のものよりも径が細く比表面積の高いｎ-ＮＣが得られれば、上記のような問題点を解決できる可能性があることを着想した。 The inventors of the present invention have problems that the conventional NC has a large specific surface area, so that the combustion performance is not sufficient, and that it is difficult to apply to crackers and explosives used in smoke fires. Recognized that it exists. The inventors have conceived that the above problems may be solved if an n-NC having a smaller diameter and a higher specific surface area than the conventional one can be obtained.
本発明は、上述のような従来技術の問題点についての認識やそれらの問題点を解決しようとする着想を背景としてなされたものであり、従来のものよりもBET比表面積の高いｎ-ＮＣの製造方法を提供することを課題とする。
また、本発明は、従来のものよりもBET比表面積の高いｎ-ＮＣを提供することを課題とする。
The present invention has been made based on the recognition of the problems of the prior art as described above and the idea of solving those problems, and the n-NC having a higher BET specific surface area than the conventional one. It is an object to provide a manufacturing method.
Another object of the present invention is to provide an n-NC having a BET specific surface area higher than that of the conventional one.
本発明者は、上述のような課題のもとでの研究過程で、エレクトロスピニング法や滴下法について検討したが、次のような問題点を認識した。
（ア）エレクトロスピニング法で製造されるＮＣは、径が90〜500nm程度、比表面積は4.8〜26.9m2/g程度であり、径が50nm以下や比表面積が80m2/g以上のものは製造できない。
（イ）エレクトロスピニング法では、高電圧を印加するので、火薬を製造する際には、発火爆発に対する安全対策が不可欠である。
（ウ）エレクトロスピニング法では、紡糸前に一旦溶媒に溶解する必要があるが、特殊な溶媒が必要であるし、さらに、ニトロ化が低いものは溶解が困難であるので、用途に合わせた様々なニトロ化の(窒素量の)ＮＣを製造することは困難である。
（エ）滴下法では、製造されるＮＣの比表面積は4〜18.2m2/g程度に過ぎず、また、大量生産に向かない手法である。
The present inventor examined the electrospinning method and the dropping method in the course of research under the above-mentioned problems, and recognized the following problems.
(A) NC produced by electrospinning has a diameter of about 90～500Nm, the specific surface area is about 4.8~26.9m 2 / g, the diameter of 50nm or less and a specific surface area of 80 m 2 / g or more of It cannot be manufactured.
(B) Since a high voltage is applied in the electrospinning method, safety measures against ignition explosion are indispensable when producing explosives.
(C) In the electrospinning method, it is necessary to dissolve once in a solvent before spinning, but a special solvent is required, and furthermore, those with low nitration are difficult to dissolve. It is difficult to produce a highly nitrated (nitrogen content) NC.
(D) In the dropping method, the specific surface area of the produced NC is only about 4 to 18.2 m 2 / g, and is not suitable for mass production.
本発明者は、さらに検討を進め、ＮＣの原料のセルロースとして従来全く使用されなかったナノセルロースゲル(以下「ｎ-Ｃゲル」ということがある)を用いること、ｎ-Ｃゲルをニトロ化する前に、硫酸で前処理を行うことで、ｎ-Ｃゲルの膨潤を促進させニトロ化の進行に効果があること、ニトロ化の際にもセルロースがナノ構造を有するためニトロ化率が高まる可能性があること、製造されるｎ-ＮＣは比表面積が大きいため、燃焼性能の向上が期待できることなどの着想を得た。そして、本発明者は、ｎ-Ｃゲルを原料としてBET比表面積の高いｎ-ＮＣを製造できることを知見した。 The present inventor has further studied and uses a nanocellulose gel (hereinafter sometimes referred to as “n-C gel”) that has never been used as cellulose as a raw material for NC, and nitrates the n-C gel. Pretreatment with sulfuric acid promotes the swelling of n-C gel and is effective in the progress of nitration, and the nitration rate can be increased because cellulose has a nanostructure during nitration. The idea was that the n-NC to be produced has a large specific surface area, so that improvement in combustion performance can be expected. And this inventor discovered that n-NC with a high BET specific surface area can be manufactured from n-C gel as a raw material.
本発明は、上記のような認識や着想、知見などに基づくものであり、この出願によれば、以下の発明が提供される。
＜１＞BET比表面積が50〜900m2/gであるナノニトロセルロース。
＜２＞窒素量が6.76〜14.14%である＜１＞に記載のナノニトロセルロース。
＜３＞直径が14〜30nmの繊維状である＜１＞又は＜２＞に記載のナノニトロセルロース。
＜４＞ナノセルロースゲルを硫酸で前処理した後、硫酸と硝酸との混酸でニトロ化するナノニトロセルロースの製造方法。
＜５＞前記前処理の硫酸として濃度25〜75％のものを用いる＜４＞に記載のナノニトロセルロースの製造方法。
＜６＞前記ニトロ化を自転・公転ミキサー内で行う＜４＞又は＜５＞に記載のナノニトロセルロースの製造方法。
＜７＞＜４＞〜＜６＞のいずれか１項に記載のナノニトロセルロースの製造方法において、ニトロ化後の洗浄工程と乾燥工程を含むナノニトロセルロースの製造方法。
＜８＞＜１＞〜＜３＞のいずれか１項に記載のナノニトロセルロースを有効成分とする無煙火薬。
The present invention is based on the above recognition, idea, knowledge and the like. According to this application, the following invention is provided.
<1> Nano nitrocellulose having a BET specific surface area of 50 to 900 m 2 / g.
<2> The nano nitrocellulose according to <1>, wherein the nitrogen amount is 6.76 to 14.14%.
<3> The nano nitrocellulose according to <1> or <2>, which has a fiber shape with a diameter of 14 to 30 nm.
<4> A method for producing nanonitrocellulose, wherein a nanocellulose gel is pretreated with sulfuric acid and then nitrated with a mixed acid of sulfuric acid and nitric acid.
<5> The method for producing nanonitrocellulose according to <4>, wherein sulfuric acid having a concentration of 25 to 75% is used as the pretreatment sulfuric acid.
<6> The method for producing nanonitrocellulose according to <4> or <5>, wherein the nitration is performed in a rotation / revolution mixer.
<7> The method for producing nanonitrocellulose according to any one of <4> to <6>, comprising a washing step after nitration and a drying step.
<8> A smokeless explosive comprising the nano nitrocellulose according to any one of <1> to <3> as an active ingredient.
本発明は、次のような態様を含むことができる。
＜９＞窒素量が9〜13.7％である＜２＞に記載のナノニトロセルロース。
＜１０＞BET比表面積が100〜130m2/gである＜１＞又は＜２＞に記載のナノニトロセルロース。
＜１１＞硫酸前処理を複数回行う＜４＞又は＜５＞に記載のナノニトロセルロースの製造方法。
＜１２＞ニトロ化に用いる硫酸と硝酸の濃度100％換算での量比が硝酸：硫酸＝10:90〜30:70である＜４＞〜＜７＞のいずれか１項に記載のナノニトロセルロースの製造方法。
＜１３＞ニトロ化に用いる混酸の硫酸と硝酸の濃度100％に換算した合計量に対するナノセルロースゲル量の比が0.05〜0.40g/mLである＜４＞〜＜７＞のいずれか１項に記載のナノニトロセルロースの製造方法。
＜１４＞ニトロ化処理時間が10〜60分である＜４＞〜＜７＞のいずれか１項に記載のナノニトロセルロースの製造方法。
The present invention can include the following aspects.
<9> The nano nitrocellulose according to <2>, wherein the nitrogen content is 9 to 13.7%.
<10> The nanonitrocellulose according to <1> or <2>, wherein the BET specific surface area is 100 to 130 m 2 / g.
<11> The method for producing nanonitrocellulose according to <4> or <5>, wherein the sulfuric acid pretreatment is performed a plurality of times.
<12> The nanonitro of any one of <4> to <7>, wherein the concentration ratio of sulfuric acid and nitric acid used for nitration in terms of 100% is nitric acid: sulfuric acid = 10: 90 to 30:70 A method for producing cellulose.
<13> Any one of <4> to <7>, wherein the ratio of the amount of nanocellulose gel to the total amount of the mixed acid used in nitration converted to 100% sulfuric acid and nitric acid is 0.05 to 0.40 g / mL. The manufacturing method of nano nitrocellulose of description.
<14> The method for producing nanonitrocellulose according to any one of <4> to <7>, wherein the nitration time is 10 to 60 minutes.
本発明のｎ-ＮＣは、従来のＮＣよりも高いBET比表面積を有する。 The n-NC of the present invention has a higher BET specific surface area than a conventional NC.
本発明のｎ-ＮＣは、従来のＮＣよりも高いBET比表面積を有している。その窒素量は通常、6.76〜14.14％の範囲が理論上可能であるが、実際は9.0〜13.7％である(なお、ｎ-ＮＣを含むＮＣの窒素量の理論的最大値は14.14％で、市販のＮＣの最も高い窒素量は13.5％程度である。)。本発明のｎ-ＮＣは、好適には、直径が14〜30nmの繊維状である。
本発明のｎ-ＮＣは、高いBET比表面積を有するため、燃焼性能が良好であることが期待できる。
以下では、本発明のｎ-ＮＣの製造について説明する。なお、本明細書では、酸の濃度、窒素含有率、含水率、混合割合、みかけの収率等の％は、特に言及しない場合は質量％を意味する。また、前後２つの数値を〜で挟む数値範囲は、それらの数値である場合も含む。
The n-NC of the present invention has a higher BET specific surface area than the conventional NC. The nitrogen content is usually in the range of 6.76 to 14.14%, but is actually 9.0 to 13.7% (note that the theoretical maximum value of the nitrogen content of NC including n-NC is 14.14%, which is commercially available. The highest nitrogen content of NC is about 13.5%.) The n-NC of the present invention is preferably in the form of a fiber having a diameter of 14 to 30 nm.
Since n-NC of the present invention has a high BET specific surface area, it can be expected that the combustion performance is good.
Hereinafter, the production of the n-NC of the present invention will be described. In the present specification, “%” such as acid concentration, nitrogen content, water content, mixing ratio, and apparent yield means mass% unless otherwise specified. In addition, the numerical range in which the two numerical values before and after are included in the range includes those numerical values.
（ｎ-Ｃゲル）
本発明のｎ-ＮＣの製造方法では、出発物質としてｎ-Ｃゲルを使用する。ｎ-Ｃゲルやその調製方法は、特許第５２０６９４７号公報に記載されている。ｎ-Ｃゲル(含水率が通常94〜96％程度)は、そのまま用いるか、含水量が70％から94％未満程度まで機械的処理(圧縮)による脱水もしくは遠心脱水してから使用することが好ましい。
(N-C gel)
In the method for producing n-NC of the present invention, n-C gel is used as a starting material. The n-C gel and its preparation method are described in Japanese Patent No. 5206947. The n-C gel (water content is usually about 94 to 96%) can be used as it is, or after being dehydrated by mechanical treatment (compression) or centrifugal dewatering until the water content is about 70% to less than 94%. preferable.
（ｎ-Ｃゲルの硫酸前処理）
硫酸前処理は、ｎ-Ｃゲルの膨潤を促進させ、後述のニトロ化処理においてニトロ化の進行に効果がある。硫酸の濃度は限定するものではないが、好ましくは20〜80％、より好ましくは30〜70％である。前処理の硫酸の濃度が20％より低い場合、ニトロ化の進行効果が小さい。濃度が80％より高い場合、前処理工程やニトロ化処理工程でｎ-Ｃが溶解し、みかけの収率が低下する。
硫酸前処理を行わない場合、ｎ-Ｃはニトロ化処理によりほとんど溶解してしまい、有効なｎ-ＮＣは得られない。
(Sulfuric acid pretreatment of n-C gel)
The sulfuric acid pretreatment promotes the swelling of the n-C gel and is effective in the progress of nitration in the nitration treatment described later. The concentration of sulfuric acid is not limited, but is preferably 20 to 80%, more preferably 30 to 70%. When the concentration of sulfuric acid in the pretreatment is lower than 20%, the effect of nitration is small. When the concentration is higher than 80%, n-C is dissolved in the pretreatment step or nitration treatment step, and the apparent yield decreases.
When sulfuric acid pretreatment is not performed, n-C is almost dissolved by nitration treatment, and effective n-NC cannot be obtained.
（ニトロ化処理）
ｎ-Ｃのニトロ化処理では、硫酸前処理後のｎ-Ｃゲルに硝酸と硫酸との混酸を加え、混合、撹拌してニトロ化を進める。
混酸における硫酸:硝酸の100％濃度換算での割合は、限定するものではないが、90：10〜70：30(好ましくは、85：15〜75：25)とすることができる。混酸に使用する硝酸は、濃度が高い方が高い窒素量のｎ-ＮＣの合成に有利である。好ましい硝酸の濃度は60〜90％である。混酸に使用する硫酸は、濃度が好ましくは25〜75％のものである。
ニトロ化に用いる混酸の硫酸と硝酸の濃度100％に換算した合計量に対するナノセルロースゲル量の比は、限定するものではないが、0.05〜0.4g/ml、好ましくは0.1〜0.35g/mlとすることができる。この比が小さい方が高いみかけの収率や高い窒素量のｎ-ＮＣを得ることができる。
混酸を加えたｎ-Ｃはゲル状であるので、ニトロ化を進行させるためには、ゲル状物に対して有効な混合、撹拌手段を用いることが望ましい。そのような混合、撹拌手段としては、限定するものではないが、自転・公転ミキサーを挙げることができる。混酸・ｎ-Ｃ混合ゲルは、混合、撹拌中に昇温する場合が有るので、好ましくは40℃を超えないように間欠的又は連続的に冷却する。
(Nitration treatment)
In the nitration treatment of n-C, a mixed acid of nitric acid and sulfuric acid is added to the n-C gel after the sulfuric acid pretreatment, and the nitration proceeds by mixing and stirring.
The ratio of sulfuric acid: nitric acid in terms of 100% concentration in the mixed acid is not limited, but can be 90:10 to 70:30 (preferably 85:15 to 75:25). The nitric acid used for the mixed acid is advantageous for the synthesis of n-NC having a higher nitrogen content when the concentration is higher. A preferable concentration of nitric acid is 60 to 90%. The sulfuric acid used for the mixed acid preferably has a concentration of 25 to 75%.
The ratio of the amount of nanocellulose gel to the total amount of the mixed acid used for nitration converted to sulfuric acid and nitric acid is 100%, but is not limited, but is 0.05 to 0.4 g / ml, preferably 0.1 to 0.35 g / ml. can do. The smaller the ratio, the higher the apparent yield and the higher the amount of n-NC.
Since n-C to which a mixed acid has been added is in the form of a gel, it is desirable to use a mixing and stirring means effective for the gel in order to proceed with nitration. Such mixing and stirring means include, but are not limited to, a rotation / revolution mixer. Since the mixed acid / n-C mixed gel may be heated during mixing and stirring, it is preferably cooled intermittently or continuously so as not to exceed 40 ° C.
（ニトロ化処理後の任意工程：洗浄処理、乾燥処理）
ニトロ化処理後のｎ-ＮＣは、必要に応じて、洗浄処理や乾燥処理を行うことができる。そのような洗浄処理や乾燥処理としては、従来のニトロ化処理後のＮＣに対して採用されているものを使用することができる。
洗浄処理としては、水洗浄や煮沸洗浄があり、ｎ-ＮＣ中の混酸が除去される。
乾燥処理では、遠心脱水等の適宜の手段により脱水した後、ｎ-ＮＣが凝集しないように乾燥を行うことにより50〜900m2/gのBET比表面積のｎ-ＮＣとすることができる。そのような乾燥手段としては凍結乾燥が好ましい。
凍結乾燥では、ｎ-ＮＣ中の水分の少なくとも一部を炭素数１〜４程度の低級アルコール(例えば、メタノール、エタノール、ｎ-プロパノール、ｎ-ブタノール及びその異性体)に置換してから凍結し、真空下(1〜5Torr.好ましくは2〜4Torr)で乾燥するのが高い比表面積を得るうえで好ましい。
(Optional steps after nitration treatment: washing treatment, drying treatment)
The n-NC after the nitration treatment can be washed or dried as necessary. As such washing treatment and drying treatment, those employed for the NC after the conventional nitration treatment can be used.
The washing process includes water washing and boiling washing, and the mixed acid in n-NC is removed.
In the drying treatment, after dehydrating by an appropriate means such as centrifugal dehydration, the n-NC having a BET specific surface area of 50 to 900 m 2 / g can be obtained by drying so that n-NC does not aggregate. As such a drying means, freeze-drying is preferable.
In lyophilization, at least part of the water in n-NC is replaced with lower alcohols having about 1 to 4 carbon atoms (for example, methanol, ethanol, n-propanol, n-butanol and isomers thereof) and then frozen. In order to obtain a high specific surface area, drying under vacuum (1 to 5 Torr, preferably 2 to 4 Torr) is preferable.
（ｎ-ＮＣ）
本発明のｎ-ＮＣは、原料のｎ-Ｃとほぼ同等か又はそれよりも直径がやや細くなった繊維状のものである。それ故、そのBET比表面積は、原料のｎ-Ｃと同程度以上の50〜900m2/gとすることができる。
(N-NC)
The n-NC of the present invention is in the form of a fiber whose diameter is substantially the same as or slightly smaller than that of the raw material n-C. Therefore, the BET specific surface area can be set to 50 to 900 m 2 / g, which is equal to or higher than n-C of the raw material.
以下、実施例により本発明を更に詳細に説明する。本発明の内容はこの実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. The content of the present invention is not limited to this embodiment.
＜実施例１：ｎ-ＮＣの製造例１＞
（１）ｎ-Ｃゲルの作製
含水量が約95％のｎ-Ｃゲルを作製した。
（２）ｎ-Ｃゲルの脱水
上記(１)で作製したｎ-Ｃゲルを遠心分離機((株)久保田製作所製 テーブルトップ遠心機5420)を用いて10分間遠心脱水し、含水量が約92％の脱水ｎ-Ｃゲル(原料ゲル)を得た。
（３）硫酸前処理(２回)
上記(２)で得た脱水ｎ-Ｃゲル16gと濃度65％の硫酸16mLを自転公転ミキサー(ARE310、THINKY製)で10分間混合・撹拌した後、遠心分離機((株)久保田製作所製テーブルトップ遠心機5420)で遠心脱水し、一次硫酸前処理ｎ-Ｃゲルを得た。
この一次硫酸前処理ｎ-Ｃゲルに濃度65%の硫酸16mLを加え、再度、自転公転ミキサー(ARE310、THINKY製)で10分撹拌した後、遠心分離機((株)久保田製作所製テーブルトップ遠心機5420)で遠心脱水し、二次硫酸前処理ｎ-Ｃゲルを得た。
（４）混酸の調製
ドラフト内で、氷温に冷却しながら、表１中に記載の量の硝酸(濃度70％)に硫酸(濃度98％)を徐々に加えて混酸を調製した。調製後の混酸は4℃程度に保持した。
（５）ニトロ化
上記(３)で得られた硫酸前処理ｎ-Ｃゲルを上記(４)で調製した混酸140mLに加え、4℃程度になるまで冷却保持した。
4℃程度に保持された溶液を自転公転ミキサー(ARE310、THINKY製)、で10分間撹拌した後、温度が30℃程度まで上昇した溶液を30分間氷水で4℃程度まで冷却した。これらの撹拌と冷却を5回繰り返し、ニトロ化を完了して、未洗浄ｎ-ＮＣゲルを得た。
（６）水洗浄
上記(５)で得た未洗浄ｎ-ＮＣゲルを３Ｌ容器に入れ、純水３Ｌ程度を注水後、ガラス棒で撹拌し、ｎ-ＮＣゲルが沈殿するまで30分〜12時間放置し、上澄みを廃棄した。これらの注水、撹拌、沈殿、及び、上澄み廃棄を３〜４回繰り返し、ｎ-ＮＣゲルをpH7まで洗浄を進めた。
pH7まで洗浄を進めたｎ-ＮＣゲルを遠心分離機((株)久保田製作所製テーブルトップ遠心機5420)で5分間脱水し、水洗浄ｎ-ＮＣゲルを得た。
（７）煮沸洗浄
上記(６)で得た水洗浄ｎ-ＮＣゲル1gあたり10mL以上注水し、還流装置付のナスフラスコを用いて8時間煮沸洗浄を行った後、遠心分離機((株)久保田製作所製テーブルトップ遠心機5420)で遠心脱水した。これらの注水、煮沸洗浄、遠心脱水をpH7で安定するまで数回繰り返し、煮沸洗浄ｎ-ＮＣゲル(生成ゲル)を得た。
（８）凍結乾燥
上記(７)で得た煮沸洗浄ｎ-ＮＣゲル1gに炭素数１〜４程度の低級アルコール1mLを添加し、自転公転ミキサー(ARE310、THINKY製)で撹拌した後、遠心分離機((株)久保田製作所製テーブルトップ遠心機5420)で遠心脱水した。これらの添加、撹拌、遠心脱水を３〜４回繰り返した。
得られたｎ-ＮＣ1gに低級アルコール0.5mLを添加し、自転公転ミキサー(ARE310、THINKY製)で撹拌し、冷蔵庫に入れて冷却し、完全に凍結させた。凍結後、半解凍し、ナスフラスコに入れた状態で真空乾燥器にセットし、炭素数１〜４程度の低級アルコールと水分が完全に揮発するまで凍結乾燥を行い、羽毛状のｎ-ＮＣを得た。
（９）製造されたｎ-ＮＣについて
上記(８)で得た実験＃２７のｎ-ＮＣについて、走査型電子顕微鏡(日本電子(株)製JSM-7400)で観察したところ、平均直径は20nm程度であり、原料のｎ-Ｃと同様のナノ繊維構造を有するものであった。また、BET比表面積を測定したところ、103m2/gであり、原料のｎ-Ｃの比表面積100〜130m2/gと同程度であった。また、窒素含有量は、13.7％程度であった。
<Example 1: Production Example 1 of n-NC>
(1) Production of n-C gel An n-C gel having a water content of about 95% was produced.
(2) Dehydration of n-C gel The n-C gel prepared in (1) above was centrifuged for 10 minutes using a centrifuge (Table Top Centrifuge 5420, manufactured by Kubota Corporation), and the water content was about A 92% dehydrated n-C gel (raw material gel) was obtained.
(3) Sulfuric acid pretreatment (twice)
16 g of the dehydrated n-C gel obtained in (2) above and 16 mL of 65% sulfuric acid were mixed and stirred for 10 minutes with a rotating / revolving mixer (ARE310, manufactured by THINKY), and then a centrifuge (Table made by Kubota Corporation). Centrifugal dehydration was performed with a top centrifuge 5420) to obtain a primary sulfuric acid pretreated n-C gel.
After adding 16 mL of 65% sulfuric acid to this primary sulfuric acid pre-treated n-C gel and stirring again for 10 minutes with an auto-revolution mixer (ARE310, manufactured by THINKY), centrifuge (Table top centrifuge manufactured by Kubota Corporation) Machine 5420) to obtain a secondary sulfuric acid pretreated n-C gel.
(4) Preparation of mixed acid While cooling to ice temperature in a fume hood, sulfuric acid (concentration 98%) was gradually added to nitric acid (concentration 70%) shown in Table 1 to prepare a mixed acid. The mixed acid after preparation was kept at about 4 ° C.
(5) Nitration The sulfuric acid pretreatment n-C gel obtained in (3) above was added to 140 mL of the mixed acid prepared in (4) above, and the mixture was kept cooled until it reached about 4 ° C.
The solution maintained at about 4 ° C. was stirred for 10 minutes with a rotation and revolution mixer (ARE310, manufactured by THINKY), and then the solution whose temperature had risen to about 30 ° C. was cooled to about 4 ° C. with ice water for 30 minutes. These stirring and cooling were repeated 5 times to complete the nitration, and an unwashed n-NC gel was obtained.
(6) Water washing The unwashed n-NC gel obtained in (5) above is placed in a 3 L container, about 3 L of pure water is poured, and then stirred with a glass rod, until 30 minutes to 12 until the n-NC gel precipitates. The supernatant was discarded after standing for a period of time. These water injection, stirring, precipitation, and discarding the supernatant were repeated 3 to 4 times, and the n-NC gel was washed to pH 7.
The n-NC gel that had been washed to pH 7 was dehydrated with a centrifuge (Table Top Centrifuge 5420, manufactured by Kubota Corporation) for 5 minutes to obtain a water-washed n-NC gel.
(7) Boiling and washing After pouring water in an amount of 10 mL or more per 1 g of the water washing n-NC gel obtained in (6) above, performing boiling washing for 8 hours using a eggplant flask equipped with a reflux device, then centrifuge (Corporation) Centrifugal dehydration was performed using a table top centrifuge 5420) manufactured by Kubota Corporation. These water injection, boiling washing, and centrifugal dehydration were repeated several times until pH 7 was stabilized to obtain boiling washed n-NC gel (generated gel).
(8) Freeze-
To 1 g of the obtained n-NC, 0.5 mL of lower alcohol was added, stirred with a rotating / revolving mixer (ARE310, manufactured by THINKY), cooled in a refrigerator, and completely frozen. After freezing, half-thaw and place in an eggplant flask in a vacuum dryer, freeze-dry until the lower alcohol and water with about 1 to 4 carbon atoms are completely volatilized, and add feather-shaped n-NC. Obtained.
(9) About n-NC produced When the n-NC of Experiment # 27 obtained in (8) above was observed with a scanning electron microscope (JSM-7400 manufactured by JEOL Ltd.), the average diameter was 20 nm. It had a nanofiber structure similar to that of n-C as a raw material. Further, the BET specific surface area was measured and found to be 103 m 2 / g, which was about the same as the n-C specific surface area of the raw material of 100 to 130 m 2 / g. The nitrogen content was about 13.7%.
エレクトロスピニング法で作製したＮＣの直径Xは90〜500nmであり、ＮＣを、直径Xnm、長さYμm、密度ρ(g/cm3；通常1.65g/cm3程度)、表面積S(m2)、重量V(g)とすると、比表面積=S/V=[π・X・Y+π(X/2)^2・2]/[π(X/2)^2・Y・ρ]=4/(ρX)+2/(ρY)、ここでY≫Xであるため、比表面積≒4/(ρX)x103(m2/g)となる。該式により算出した比表面積は、4.8〜26.9m2/gであることから、本発明の実施例のｎ-ＮＣは、エレクトロスピニング法で作製したｎ-ＮＣよりも４倍程度以上の比表面積を有するものと言える。
なお、実施例１のｎ-ＮＣについて、その平均直径20nmに基づいて同様に算出した比表面積は121m2/gである。上記実測値103m2/gは、平均直径に基づく比表面積より少し低い値となっているが、これは繊維同士の多少の重なりによるものと考えられる。
下記の実施例４〜７のｎ-ＮＣについてはBET比表面積を測定していないが、その繊維の直径はｎ-Ｃと同等か又はそれより僅かに小さくなっている。それ故、凍結乾燥などの凝集が防止される乾燥方法を採用することにより、実施例１と同様のBET比表面積が得られると言える。
また、ｎ-Ｃゲルとしては繊維直径が3〜100nmのものが得られるので、それらの繊維直径のｎ-Ｃゲルを用いれば、BET比表面積が50〜900m2/gの範囲内のｎ-ＮＣを合成することも可能である。
The diameter X of the NC manufactured by electrospinning is 90～500Nm, the NC, diameter X nm, length Ymyuemu, density ρ (g / cm 3; usually 1.65 g / cm 3 or so), surface area S (m 2) of , Weight V (g), specific surface area = S / V = [π ・ X ・ Y + π (X / 2) ^ 2 ・ 2] / [π (X / 2) ^ 2 ・ Y ・ ρ] = 4 / (ρX) + 2 / (ρY), where Y >> X, so that the specific surface area≈4 / (ρX) × 10 3 (m 2 / g). Since the specific surface area calculated by this formula is 4.8 to 26.9 m 2 / g, the n-NC in the examples of the present invention is about 4 times or more the specific surface area than n-NC produced by the electrospinning method. It can be said that it has.
In addition, about n-NC of Example 1, the specific surface area calculated similarly based on the average diameter of 20 nm is 121 m < 2 > / g. The measured value 103 m 2 / g is a value slightly lower than the specific surface area based on the average diameter, which is considered to be due to a slight overlap between the fibers.
Although the BET specific surface area was not measured for the n-NC of Examples 4 to 7 below, the diameter of the fiber was equal to or slightly smaller than that of n-C. Therefore, it can be said that a BET specific surface area similar to that in Example 1 can be obtained by employing a drying method such as freeze-drying that prevents aggregation.
In addition, since n-C gels having a fiber diameter of 3 to 100 nm can be obtained, if n-C gels having those fiber diameters are used, n-C gels having a BET specific surface area in the range of 50 to 900 m 2 / g are used. It is also possible to synthesize NC.
＜実施例２：ｎ-ＮＣの示差走査熱量測定＞
実施例１の実験＃２７のｎ-ＮＣと同じ製造方法で得た、凍結乾燥ｎ-ＮＣ、および、加熱乾燥以外は実施例１と同じ製造方法で得た加熱乾燥ｎ-ＮＣ(比較例)について示差走査熱量測定を行った。測定結果を図３に示した。加熱乾燥ｎ-ＮＣについては、乾燥の際に凝集する。よって得られた試料は比表面積が小さいため、ピークが広がってしまい、火薬として性能が出せない。一方、凍結乾燥を行った凍結乾燥ｎ-ＮＣでは、鋭いピークが得られ、比表面積が大きく、火薬として性能が出せることが本結果から予想できる。
<Example 2: n-NC differential scanning calorimetry>
The freeze-dried n-NC obtained by the same production method as the n-NC of Experiment # 27 in Example 1 and the heat-dried n-NC obtained by the same production method as in Example 1 except for heat drying (Comparative Example) Was subjected to differential scanning calorimetry. The measurement results are shown in FIG. Heat-dried n-NC aggregates during drying. Therefore, since the obtained sample has a small specific surface area, the peak spreads and performance as a gunpowder cannot be achieved. On the other hand, with freeze-dried n-NC that has been freeze-dried, it can be predicted from this result that a sharp peak is obtained, the specific surface area is large, and performance as an explosive can be achieved.
＜実施例３：ｎ-ＮＣの燃焼試験＞
実施例１の実験＃２７のｎ-ＮＣ又は市販のＮＣ(窒素量13.4%)0.2gを点火装置を備えた100ccの耐圧密閉容器に導入し、密閉後点火した。図３に点火後の時間経過に伴う容器内圧力変化を示す。ｎ-ＮＣはＮＣに比べ、最高圧力が高く、また、最高圧力に達するまでの時間が短かった。このことから、ｎ-ＮＣは、ＮＣに比べ燃焼性能が向上していると考えられる。
<Example 3: n-NC combustion test>
The n-NC of Experiment # 27 of Example 1 or 0.2 g of commercially available NC (nitrogen amount 13.4%) was introduced into a 100 cc pressure-resistant airtight container equipped with an ignition device, and ignited after sealing. FIG. 3 shows a change in pressure in the container with time after ignition. n-NC had a higher maximum pressure than NC and a shorter time to reach the maximum pressure. From this, it is considered that n-NC has improved combustion performance compared to NC.
＜実施例４：ｎ-ＮＣの製造例２、硫酸前処理条件の影響調査＞
硫酸前処理の条件およびニトロ化の条件を表２のとおり変更し、実施例１の実験#２７と同様にしてｎ-ＮＣを製造した。硫酸濃度が65％で１回処理した場合にみかけの収率(＝煮沸洗浄ｎ-ＮＣゲル(生成ゲル)／脱水ｎ-Ｃゲル(原料ゲル))が最も高く210％となった。同濃度で２回処理した場合には、窒素含有率が11.6％と高くなった。
これらの実施例からみて、硫酸前処理後の水分濃度51〜60％がみかけの収率の点で好ましいと言える。また、窒素濃度を高くする点では２回処理することが好ましい。
<Example 4: Production example 2 of n-NC, investigation of influence of sulfuric acid pretreatment conditions>
The conditions for sulfuric acid pretreatment and nitration were changed as shown in Table 2, and n-NC was produced in the same manner as in Experiment # 27 of Example 1. When the sulfuric acid concentration was treated once at 65%, the apparent yield (= boiling washed n-NC gel (generated gel) / dehydrated n-C gel (raw material gel)) was the highest, 210%. When treated twice at the same concentration, the nitrogen content increased to 11.6%.
From these examples, it can be said that a water concentration of 51 to 60% after sulfuric acid pretreatment is preferable in terms of apparent yield. Moreover, it is preferable to perform the treatment twice in terms of increasing the nitrogen concentration.
＜実施例５：ｎ-ＮＣの製造例３、ニトロ化条件の影響調査１＞
ニトロ化条件における硫酸と硝酸の100％濃度換算での量比等を表３のとおりに変更し、実施例１の実験＃２７と同様にしてｎ-ＮＣを製造した。混酸に用いる硫酸量の比を高くすると高い収率が得られた。混酸に用いる硫酸量の比が８４(実験＃６)の場合、みかけの収率と窒素含有率がバランス良く、高くなった。
<Example 5: Production example 3 of n-NC,
The amount ratio of sulfuric acid and nitric acid in nitration conditions in terms of 100% concentration was changed as shown in Table 3, and n-NC was produced in the same manner as in Experiment # 27 of Example 1. A higher yield was obtained when the ratio of the amount of sulfuric acid used in the mixed acid was increased. When the ratio of the amount of sulfuric acid used for the mixed acid was 84 (Experiment # 6), the apparent yield and the nitrogen content were well balanced and increased.
＜実施例６：ｎ-ＮＣの製造例４、ニトロ化条件の影響調査２＞
ニトロ化条件におけるｎ-Ｃゲル量の混酸(100％濃度換算)量に対する比等を表４のとおりに変更し、実施例１の実験＃２７と同様にしてｎ-ＮＣを製造した。用いるｎ-Ｃの量を少なくすると、収率や窒素含有率が高くなった。その傾向は、ｎ-Ｃゲル／混酸の比が0.2g/ml以下の場合に特に著しい。
<Example 6: Production example 4 of n-NC, investigation 2 of influence of nitration conditions>
The ratio of the amount of n-C gel to the amount of mixed acid (converted to 100% concentration) under nitration conditions was changed as shown in Table 4, and n-NC was produced in the same manner as in Experiment # 27 of Example 1. When the amount of n-C used was reduced, the yield and nitrogen content increased. This tendency is particularly remarkable when the ratio of n-C gel / mixed acid is 0.2 g / ml or less.
＜実施例７：ｎ-ＮＣの製造例５、ニトロ化条件の影響調査３＞
ニトロ化条件における反応時間を表５のとおりに変更し、実施例１の実験＃２７と同様にしてｎ-ＮＣを製造した。反応時間が45分の場合に収率や窒素含有率が最も高くなった。反応時間が90分程度以上に長くなると、収率や窒素含有率が45分の場合よりも低くなった。これらのことから、高いみかけの収率を得るニトロ化処理時間は10〜30分(好ましくは10〜20分)であり、高い窒素含有率を得るニトロ化処理時間は30〜60分(好ましくは40〜50分)であると言える。
<Example 7: Production example 5 of n-NC, influence investigation 3 of nitration conditions>
The reaction time under nitration conditions was changed as shown in Table 5, and n-NC was produced in the same manner as in Experiment # 27 of Example 1. When the reaction time was 45 minutes, the yield and nitrogen content were the highest. When the reaction time was longer than about 90 minutes, the yield and nitrogen content were lower than in the case of 45 minutes. From these facts, the nitration time to obtain a high apparent yield is 10 to 30 minutes (preferably 10 to 20 minutes), and the nitration time to obtain a high nitrogen content is 30 to 60 minutes (preferably 40-50 minutes).
本発明のｎ-ＮＣは、従来のものよりも高いBET比表面積を有するものであり、無煙火薬、塗料、医薬、接着剤、セルロイド等の分野において利用することが期待される。 The n-NC of the present invention has a higher BET specific surface area than conventional ones, and is expected to be used in the fields of smokeless explosives, paints, medicines, adhesives, celluloids and the like.
Claims (8)
The smokeless explosive which uses the nano nitrocellulose of any one of Claims 1-3 as an active ingredient.
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| WO2023070185A1 (en) * | 2021-10-25 | 2023-05-04 | Cnpem - Centro Nacional De Pesquisa Em Energia E Materiais | Porous foam for retaining organic and inorganic compounds, method for producing same and uses thereof |
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| KR102515525B1 (en) * | 2022-01-10 | 2023-03-29 | 제이엔케이에너지 주식회사 | The nitrocellous production method for reducing environmental pollution and isopropyl alcohol used nitrocellous production recycling method |
| WO2023132469A1 (en) * | 2022-01-10 | 2023-07-13 | 제이엔케이에너지 주식회사 | Preparation method for nitrocellulose for reducing environmental pollution and isopropyl alcohol recycling method used for preparation of nitrocellulose |
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