技术领域technical field
本发明涉及一种叠氮纤维素硝酸酯的制备方法，具体涉及一种用微波辐射将硝化纤维素直接叠氮化的制备方法。The invention relates to a preparation method of azide cellulose nitrate, in particular to a preparation method of direct azidation of nitrocellulose by microwave radiation.
背景技术Background technique
自1864年叠氮基被发现以来，人们对叠氮化合物进行了大量的研究。其原因是叠氮化合物一方面在发射药和推进剂的应用上，不仅能量水平高,而且燃烧产物分子量低，不产生烟雾。既有利于提高推进剂的能量和燃速，又能降低推进剂的火焰温度和烟雾信号。而且大部分叠氮化合物的撞击和摩擦感度较低，比较安全。另一方面，由于近年来,点击化学以其应用范围广、反应条件简单、速度快,产率高、环境友好、选择性强等诸多优点受到科学家的青睐；在药物开发和生物医用材料，聚合物材料表面改性、复杂结构大分子的构架、制备混合生物材料等诸多领域中,已成为目前最有应用前途的合成理念之一。其中，叠氮化合物与末端炔在Cu(I)催化下生成1,2，3—三唑化合物，即Cu(I)催化的Huisgen1，3-偶极环加成反应，是目前研究和应用最多的点击化学。这也大大拓宽了叠氮化合物的应用范围。Since the discovery of the azido group in 1864, a great deal of research has been done on azides. The reason is that on the one hand, azide compounds not only have high energy levels in the application of propellants and propellants, but also have low molecular weight combustion products and do not produce smoke. Not only is it beneficial to increase the energy and burning rate of the propellant, but it can also reduce the flame temperature and smoke signal of the propellant. Moreover, most azides have low impact and friction sensitivity and are relatively safe. On the other hand, in recent years, click chemistry has been favored by scientists for its wide application range, simple reaction conditions, fast speed, high yield, environmental friendliness, and strong selectivity; in drug development and biomedical materials, polymerization It has become one of the most promising synthetic concepts in many fields such as surface modification of biomaterials, framework of complex structural macromolecules, and preparation of hybrid biomaterials. Among them, Cu(I)-catalyzed Huisgen1,3-dipolar cycloaddition reaction of azide compound and terminal alkyne to generate 1,2,3-triazole compound is the most researched and applied at present. click chemistry. This also greatly broadens the scope of application of azide compounds.
作为自然界蕴含量最为丰富的天然高分子材料，纤维素经过不同的方法进行功能化以后，获得了多种可以满足不同应用的纤维素醚类和酯类衍生物。其中纤维素硝酸酯(或称硝化纤维素)是应用最为广泛的纤维素衍生物之一，该产品根据其酯化度(即氮含量)的不同，应用于涂料、纤维、胶片、火炸药等不同领域。若在纤维素硝酸酯上进一步引入叠氮基，不仅可以增加氮含量，而且可以利用引入的叠氮基通过点击化学再次引入新的基团对纤维素硝酸酯进行改性。叠氮纤维素硝酸酯可以通过将纤维素甲磺酸酯或纤维素对甲苯磺酸酯与叠氮金属化合物进行反应制备叠氮纤维素，再进一步硝化制得[Carignan，1988，USH430]，但该方法最大的缺点是反应时间长、反应物料利用率低、且产物溶解性能差；也可以直接将纤维素硝酸酯与碘化钾和叠氮化物进行反应制备[Gilbert，1989，US4849514]，但该方法最大的缺点是所得产物仍残留卤素，难以除去。As the most abundant natural polymer material in nature, cellulose has been functionalized by different methods to obtain a variety of cellulose ether and ester derivatives that can meet different applications. Among them, cellulose nitrate (or nitrocellulose) is one of the most widely used cellulose derivatives. According to the degree of esterification (that is, nitrogen content), this product is used in coatings, fibers, films, explosives, etc. different area. If the azide group is further introduced on the cellulose nitrate, not only the nitrogen content can be increased, but also the introduced azide group can be used to introduce new groups through click chemistry to modify the cellulose nitrate. Azidocellulose nitrate can be prepared by reacting cellulose mesylate or cellulose p-toluenesulfonate with azide metal compound to prepare azidocellulose, and then further nitrated [Carignan, 1988, USH430], but The biggest disadvantage of this method is that the reaction time is long, the utilization rate of reaction materials is low, and the product solubility is poor; it is also possible to directly prepare cellulose nitrate with potassium iodide and azide [Gilbert, 1989, US4849514], but the method The biggest disadvantage is that the resulting product still has residual halogens, which are difficult to remove.
上述制备叠氮纤维素硝酸酯的方法均有反应时间长、产物收率和纯度不高的缺点，而且制得的产品的性能差，只能在高温下溶解在N,N-二甲基甲酰胺(DMF)，二甲基亚砜(DMSO)这两种强极性溶剂中，不能很好的满足应用要求。迄今为止，利用微波辐射制备叠氮纤维素硝酸酯的方法尚未见报道。The above-mentioned method for preparing azide cellulose nitrate all has the disadvantages of long reaction time, low product yield and low purity, and the performance of the obtained product is poor, and can only be dissolved in N,N-dimethyl formaldehyde at high temperature. Amide (DMF) and dimethyl sulfoxide (DMSO), which are two strong polar solvents, cannot meet the application requirements well. So far, the preparation of azidocellulose nitrate by microwave irradiation has not been reported.
发明内容Contents of the invention
本发明的目的是提供一种生产工艺简单、原料不易降解、产品溶解性能和加工性能好的。The object of the present invention is to provide a product with simple production process, difficult degradation of raw materials, and good solubility and processability of the product.
本发明是通过如下技术方案来实现的：The present invention is achieved through the following technical solutions:
一种叠氮纤维素硝酸酯的微波合成方法包括步骤：A microwave synthesis method of azide cellulose nitrate comprises steps:
(1)溶解：将硝化纤维素溶解于有机溶剂中；(1) Dissolving: dissolving nitrocellulose in an organic solvent;
(2)微波加热反应：步骤(1)所得溶液与碱金属叠氮化物混合于微波加热仪防爆试管中，置于微波加热仪中，磁力搅拌，微波加热反应得到红棕色黏稠状液体；(2) Microwave heating reaction: the solution obtained in step (1) is mixed with an alkali metal azide in an explosion-proof test tube of a microwave heater, placed in a microwave heater, magnetically stirred, and reacted by microwave heating to obtain a reddish-brown viscous liquid;
(3)洗涤干燥。(3) Wash and dry.
实质上，整个反应过程是将硝化纤维(即纤维素硝酸酯)先溶解于有机溶剂中，再将其与碱金属叠氮化物如叠氮化钠、叠氮化钾等混合，用微波加热反应，最后经溶剂洗涤干燥后即得产品。In essence, the whole reaction process is to dissolve nitrocellulose (ie, cellulose nitrate) in an organic solvent, then mix it with an alkali metal azide such as sodium azide, potassium azide, etc., and use microwave heating to react , and finally the product is obtained after solvent washing and drying.
进一步的，所述步骤(2)中微波加热参数为功率100-250W，温度50-100℃，微波加热时间5-15min。Further, the microwave heating parameters in the step (2) are power 100-250W, temperature 50-100°C, microwave heating time 5-15min.
进一步优选的，所述步骤(2)中微波加热参数为功率150W，温度75℃，微波加热时间5min。该条件为反应最优参数，反应时间最短且产品溶解性能最好。Further preferably, the microwave heating parameters in the step (2) are 150W power, 75°C temperature, and 5min microwave heating time. This condition is the optimal parameter for the reaction, the reaction time is the shortest and the product solubility is the best.
进一步优选的，所述步骤(2)中碱金属叠氮化物为叠氮化钠。Further preferably, the alkali metal azide in the step (2) is sodium azide.
进一步的，所述步骤(2)中碱金属叠氮化物中叠氮基与硝化纤维素中硝基的摩尔比为0.5-6:1。Further, the molar ratio of the azido group in the alkali metal azide to the nitro group in the nitrocellulose in the step (2) is 0.5-6:1.
进一步优选的，所述步骤(2)中先将碱金属叠氮化物溶解在有机溶剂中，再与硝化纤维素溶液混合。即在与硝化纤维混合之前先将碱金属叠氮化物溶解于有机溶剂之中。Further preferably, in the step (2), the alkali metal azide is first dissolved in an organic solvent, and then mixed with the nitrocellulose solution. That is, the alkali metal azide is dissolved in an organic solvent before being mixed with nitrocellulose.
进一步的，所述有机溶剂为N,N-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、乙腈、丙酮、乙醚/乙醇、乙腈/丁醇中的一种。Further, the organic solvent is one of N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), acetonitrile, acetone, ether/ethanol, and acetonitrile/butanol.
进一步优选的，所述步骤(3)为待冷却后缓慢倒入蒸馏水洗涤，生成大量沉淀，过滤收集固体；再用DMF溶解，然后用蒸馏水沉淀，过滤；重复三次，真空干燥后得到叠氮纤维素硝酸脂产物。Further preferably, the step (3) is slowly poured into distilled water for washing after cooling to generate a large amount of precipitate, and the solid is collected by filtration; then dissolved with DMF, then precipitated with distilled water, filtered; repeated three times, and obtained azide fiber after vacuum drying nitrate products.
本发明具有如下有益效果：The present invention has following beneficial effects:
1、本发明以纤维素硝酸酯为原料，直接与叠氮化钠在微波作用下反应合成了叠氮纤维素硝酸酯，一步到位，省去中间合成步骤，直接将反应时间从数小时缩短到几分钟，节省了大量时间，大大缩短了生产周期。1. The present invention uses cellulose nitrate as a raw material, and directly reacts with sodium azide to synthesize cellulose azide nitrate under the action of microwaves. One step is in place, and intermediate synthesis steps are omitted, and the reaction time is directly shortened from several hours to A few minutes, saving a lot of time and greatly shortening the production cycle.
2、采用本发明提供的方法制得的产物因为省去了中间合成步骤，其纯度大大提高，同时，本发明的叠氮纤维素硝酸酯能在室温下快速溶解在丙酮、乙腈、DMF、DMSO等有机溶剂中，溶解性能好，能很好满足应用要求，而且原料来源广泛且具有可再生性。2, adopt the product that the method provided by the present invention makes because have saved intermediate synthetic steps, its purity improves greatly, simultaneously, azide cellulose nitrate of the present invention can be dissolved in acetone, acetonitrile, DMF, DMSO rapidly at room temperature In other organic solvents, it has good solubility and can well meet the application requirements, and the raw materials have a wide range of sources and are renewable.
具体实施方式Detailed ways
下面结合具体实施例对本发明做进一步说明。所述实施例仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The present invention will be further described below in conjunction with specific embodiments. The described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.
实施例1Example 1
1g氮含量为11.56％硝化纤维素溶解于15g的乙腈形成透明溶液。将一定过量的叠氮化钠与硝化纤维素溶液混合于微波加热仪防爆试管中，置于微波加热仪中，磁力搅拌，加热程序设定为100W，加热到55℃保持5min，得到红棕色黏稠状液体。待冷却后缓慢倒入100ml蒸馏水，生成大量沉淀，过滤收集固体；再用15mlDMF溶解，并用100ml蒸馏水沉淀，过滤；重复三次，真空干燥后得到0.43g叠氮纤维素硝酸脂产物，经元素分析测试含氮量为14.07％，计算取代度为0.21。1 g of nitrocellulose with a nitrogen content of 11.56% was dissolved in 15 g of acetonitrile to form a transparent solution. Mix a certain amount of sodium azide and nitrocellulose solution in an explosion-proof test tube of a microwave heater, place it in a microwave heater, stir it magnetically, set the heating program to 100W, heat to 55°C for 5 minutes, and obtain a reddish-brown viscous like liquid. Slowly pour 100ml of distilled water after cooling to form a large amount of precipitate, collect the solid by filtration; then dissolve it with 15ml of DMF, precipitate with 100ml of distilled water, and filter; repeat three times, and obtain 0.43g of azide cellulose nitrate product after vacuum drying, which is tested by elemental analysis The nitrogen content is 14.07%, and the calculated degree of substitution is 0.21.
实施例2Example 2
1g氮含量为10.87％硝化纤维素溶解于15g的N，N-二甲基甲酰胺(DMF)形成透明溶液。将一定过量的叠氮化钠与硝化纤维素溶液混合于微波加热仪防爆试管中，置于微波加热仪中，磁力搅拌，加热程序设定为100W，加热到55℃保持10min，得到红棕色黏稠状液体。后处理方法同实施例一，最终得到0.49g叠氮纤维素硝酸脂产物，经元素分析测试含氮量为14.33％，计算取代度为0.28。1 g of nitrocellulose with a nitrogen content of 10.87% was dissolved in 15 g of N,N-dimethylformamide (DMF) to form a transparent solution. Mix a certain amount of sodium azide and nitrocellulose solution in an explosion-proof test tube of a microwave heater, place it in a microwave heater, stir it magnetically, set the heating program to 100W, heat it to 55°C for 10 minutes, and obtain a reddish-brown viscous like liquid. The post-processing method is the same as that in Example 1, and finally 0.49 g of azide cellulose nitrate product is obtained. The nitrogen content is 14.33% as tested by elemental analysis, and the calculated substitution degree is 0.28.
实施例3Example 3
1g氮含量为9.75％硝化纤维素溶解于15g的二甲基亚砜(DMSO)形成透明溶液。将一定过量的叠氮化钠与硝化纤维素溶液混合于微波加热仪防爆试管中，置于微波加热仪中，磁力搅拌，加热程序设定为150W，加热到75℃保持5min，得到红棕色黏稠状液体。后处理方法同实施例一，最终得到0.58g叠氮纤维素硝酸脂产物，经元素分析测试含氮量为18.33％，计算取代度为0.64。1 g of nitrocellulose with a nitrogen content of 9.75% was dissolved in 15 g of dimethyl sulfoxide (DMSO) to form a transparent solution. Mix a certain amount of sodium azide and nitrocellulose solution in an explosion-proof test tube of a microwave heater, place it in a microwave heater, stir it magnetically, set the heating program to 150W, heat to 75°C for 5 minutes, and obtain a reddish-brown viscous like liquid. The post-processing method is the same as that in Example 1, and finally 0.58 g of azide cellulose nitrate product is obtained. The nitrogen content is 18.33% as tested by elemental analysis, and the calculated substitution degree is 0.64.
实施例4Example 4
1g氮含量为8.84％硝化纤维素溶解于15g的二甲基亚砜(DMSO)形成透明溶液。将一定过量的叠氮化钠与硝化纤维素溶液混合于微波加热仪防爆试管中，置于微波加热仪中，磁力搅拌，加热程序设定为150W，加热到75℃保持10min，得到红棕色黏稠状液体。后处理方法同实施例一，最终得到0.62g叠氮纤维素硝酸脂产物，经元素分析测试含氮量为16.78％，计算取代度为0.56。1 g of nitrocellulose with a nitrogen content of 8.84% was dissolved in 15 g of dimethyl sulfoxide (DMSO) to form a transparent solution. Mix a certain amount of sodium azide and nitrocellulose solution in an explosion-proof test tube of a microwave heater, place it in a microwave heater, stir it magnetically, set the heating program to 150W, heat to 75°C for 10 minutes, and obtain a reddish-brown viscous like liquid. The post-processing method is the same as that in Example 1, and finally 0.62 g of azide cellulose nitrate product is obtained. The nitrogen content is 16.78% as tested by elemental analysis, and the calculated substitution degree is 0.56.
实施例5Example 5
1g氮含量为7.38％硝化纤维素溶解于15g的形成N，N-二甲基甲酰胺(DMF)透明溶液。将一定过量的叠氮化钠与硝化纤维素溶液混合于微波加热仪防爆试管中，置于微波加热仪中，磁力搅拌，加热程序设定为200W，加热到95℃保持5min，得到红棕色黏稠状液体。后处理方法同实施例一，最终得到0.66g叠氮纤维素硝酸脂产物，经元素分析测试含氮量为13.12％，计算取代度为0.36。1 g of nitrocellulose with a nitrogen content of 7.38% was dissolved in 15 g of N,N-dimethylformamide (DMF) clear solution. Mix a certain amount of sodium azide and nitrocellulose solution in an explosion-proof test tube of a microwave heater, place it in a microwave heater, stir it magnetically, set the heating program to 200W, heat to 95°C for 5 minutes, and obtain a reddish-brown viscous like liquid. The post-processing method is the same as that in Example 1, and finally 0.66 g of azide cellulose nitrate product is obtained. The nitrogen content is 13.12% as tested by elemental analysis, and the calculated substitution degree is 0.36.
实施例6Example 6
1g氮含量为6.12％硝化纤维素溶解于15g的二甲基亚砜(DMSO)形成透明溶液。将一定过量的叠氮化钠与硝化纤维素溶液混合于微波加热仪防爆试管中，置于微波加热仪中，磁力搅拌，加热程序设定为200W，加热到95℃保持10min，得到红棕色黏稠状液体。后处理方法同实施例一，最终得到0.69g叠氮纤维素硝酸脂产物，经元素分析测试含氮量为11.02％，计算取代度为0.30。1 g of nitrocellulose with a nitrogen content of 6.12% was dissolved in 15 g of dimethyl sulfoxide (DMSO) to form a transparent solution. Mix a certain amount of sodium azide and nitrocellulose solution in an explosion-proof test tube of a microwave heater, place it in a microwave heater, stir it magnetically, set the heating program to 200W, heat to 95°C for 10 minutes, and obtain a reddish-brown viscous like liquid. The post-processing method is the same as that in Example 1, and finally 0.69 g of azide cellulose nitrate product is obtained. The nitrogen content is 11.02% as tested by elemental analysis, and the calculated substitution degree is 0.30.
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| CN108727216A (en)* | 2018-07-13 | 2018-11-02 | 南京工业大学 | Method for synthesizing α -diazo ester compound by using microwave under normal pressure |
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| US4849514A (en)* | 1988-03-07 | 1989-07-18 | The United States Of America As Represented By The Secretary Of The Army | Process for making azidodeoxycellulose |
| CN1569901A (en)* | 2004-04-30 | 2005-01-26 | 北京理工大学 | Azido dihydroxypropyl cellulose nitrate preparation method and synthesis |
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| US4568399A (en)* | 1985-03-22 | 1986-02-04 | The United States Of America As Represented By The Secretary Of The Army | Propellant compositions |
| US4849514A (en)* | 1988-03-07 | 1989-07-18 | The United States Of America As Represented By The Secretary Of The Army | Process for making azidodeoxycellulose |
| CN1569901A (en)* | 2004-04-30 | 2005-01-26 | 北京理工大学 | Azido dihydroxypropyl cellulose nitrate preparation method and synthesis |
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| 张弛等: "微波合成聚叠氮缩水甘油醚的研究", 《化工新型材料》* |
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| CN108727216A (en)* | 2018-07-13 | 2018-11-02 | 南京工业大学 | Method for synthesizing α -diazo ester compound by using microwave under normal pressure |
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| Date | Code | Title | Description |
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| C06 | Publication | ||
| PB01 | Publication | ||
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| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication | Application publication date:20151209 |