CN102558368A - Preparation method of oxidized regenerated cellulose (ORC) absorbable hemostasis material - Google Patents
Preparation method of oxidized regenerated cellulose (ORC) absorbable hemostasis material Download PDFInfo
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- 239000004627 regenerated cellulose Substances 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000023597 hemostasis Effects 0.000 title abstract 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000003647 oxidation Effects 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 30
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims abstract description 24
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims abstract description 24
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 230000002439 hemostatic effect Effects 0.000 claims description 29
- 230000001590 oxidative effect Effects 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 9
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 20
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 5
- 239000004744 fabric Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 2
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- 230000000052 comparative effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
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Abstract
Description
技术领域 technical field
本发明涉及一种氧化再生纤维素可吸收止血材料的制备方法。The invention relates to a preparation method of oxidized regenerated cellulose absorbable hemostatic material.
背景技术 Background technique
氧化再生纤维素(ORC)是以再生纤维素为原材料，经过合适的氧化体系对再生纤维素进行处理，将纤维素分子结构中的伯羟基官能团可控氧化成羧基官能团，使产物中的含量达到16％～24％，最后再经过洗涤、干燥、封装、灭菌等过程即可制备出医用可吸收止血材料。Oxidized regenerated cellulose (ORC) is based on regenerated cellulose as raw material, and the regenerated cellulose is treated with a suitable oxidation system to oxidize the primary hydroxyl functional groups in the molecular structure of cellulose into carboxyl functional groups in a controlled manner, so that the content in the product reaches 16% to 24%, and finally the medical absorbable hemostatic material can be prepared through washing, drying, packaging, sterilization and other processes.
多年以来，氧化再生纤维素因其优异的止血性能和生物可吸收性能而受到化学、生物、医学等多领域研究人员的关注。最早被发现对氧化再生纤维素的伯羟基具有选择性氧化作用的氧化剂为二氧化氮，但是采用气态二氧化氮对再生纤维素进行氧化时，氧化体系中放热现象剧烈，导致产物的聚合度大幅度降解，甚至导致纤维强度大大降低以致材料无法满足实际应用的要求。因此，液相二氧化氮/惰性溶剂体系被研发出来，其中，二氧化氮依然作为氧化剂，惰性溶剂则将二氧化氮溶解构成液相氧化体系，从而使反应条件变得温和，缓解了反应过程中的放热效应，同时再生纤维素的氧化效率得到提升，进而在较短的时间内便可以制备羧基含量介于16％～24％的氧化再生纤维素可吸收止血材料，而且材料具有适宜的强度。For many years, oxidized regenerated cellulose has attracted the attention of researchers in many fields such as chemistry, biology, and medicine because of its excellent hemostatic properties and bioabsorbable properties. Nitrogen dioxide was the first oxidant that was found to selectively oxidize the primary hydroxyl groups of oxidized regenerated cellulose. However, when gaseous nitrogen dioxide was used to oxidize regenerated cellulose, the exothermic phenomenon in the oxidation system was severe, resulting in a high degree of polymerization of the product. Substantial degradation, and even lead to a great reduction in fiber strength so that the material can not meet the requirements of practical applications. Therefore, a liquid-phase nitrogen dioxide/inert solvent system was developed, in which nitrogen dioxide is still used as an oxidant, and the inert solvent dissolves nitrogen dioxide to form a liquid-phase oxidation system, thereby making the reaction conditions milder and easing the reaction process. At the same time, the oxidation efficiency of regenerated cellulose is improved, and then the oxidized regenerated cellulose absorbable hemostatic material with carboxyl content between 16% and 24% can be prepared in a short period of time, and the material has suitable strength .
常规的氧化再生纤维素可吸收止血材料的制备方法中普遍采用全氟化碳(PFCs)等消耗臭氧层物质(ODSs)。该类物质会引起气候变化，对环境造成严重影响。而且，全氟化碳的价格相对更为昂贵，进而会导致氧化再生纤维素可吸收止血材料的生产成本大大增加，最终会加重使用此种材料的病人的经济负担。Ozone-depleting substances (ODSs) such as perfluorocarbons (PFCs) are commonly used in conventional preparation methods of oxidized regenerated cellulose absorbable hemostatic materials. Such substances can cause climate change and have serious impacts on the environment. Moreover, the price of perfluorocarbons is relatively more expensive, which will lead to a significant increase in the production cost of the oxidized regenerated cellulose absorbable hemostatic material, which will eventually increase the financial burden on patients who use this material.
新型氧化剂TEMPO的氧化效率较高，且TEMPO对环境及气候的影响较小。但是，其氧化产物要经过酸处理和离子化稳定处理过程，并且TEMPO的价格也比较昂贵，致使氧化再生纤维素的成本大幅度上升。更为重要的是，经过TEMPO体系氧化之后，纤维织物的成型性很差，很容易造成织物破损，无法进行临床使用，所以TEMPO体系的技术转化较为困难。The oxidation efficiency of the new oxidant TEMPO is higher, and TEMPO has less impact on the environment and climate. However, the oxidation product has to undergo acid treatment and ionization stabilization treatment, and the price of TEMPO is also relatively expensive, resulting in a substantial increase in the cost of oxidized regenerated cellulose. More importantly, after the TEMPO system is oxidized, the formability of the fiber fabric is very poor, it is easy to cause fabric damage, and it cannot be used clinically, so the technical transformation of the TEMPO system is relatively difficult.
发明内容 Contents of the invention
本发明是要解决现有氧化再生纤维素可吸收止血材料的制备方法成本高，污染环境，反应过程难以控制，不适于产业化生产的问题，提供一种氧化再生纤维素可吸收止血材料的制备方法。The present invention aims to solve the problems that the existing preparation method of oxidized regenerated cellulose absorbable hemostatic material has high cost, pollutes the environment, the reaction process is difficult to control, and is not suitable for industrial production, and provides a preparation method of oxidized regenerated cellulose absorbable hemostatic material method.
本发明氧化再生纤维素可吸收止血材料的制备方法，按以下步骤进行：一、将二氧化氮和环己烷加入到循环反应器中，形成氧化液，氧化液中二氧化氮的质量百分比浓度为5％～75％，然后再加入再生纤维素，使再生纤维素完全浸泡在氧化液中，密封反应器，于5～45℃反应时间1～72h，得氧化产物；二、用环己烷冲洗氧化产物2～5次，然后使用体积浓度为20％～95％的乙醇水溶液冲洗氧化产物2～3次，再用无水乙醇冲洗氧化产物3～5次；三、然后将无水乙醇冲洗后的氧化产物置于-80～-10℃冷冻干燥，干燥时间为24～72h，即得到氧化再生纤维素可吸收止血材料；其中步骤一中再生纤维素与氧化液中二氧化氮的质量比为0.01～100∶1。The preparation method of the oxidized regenerated cellulose absorbable hemostatic material of the present invention is carried out according to the following steps: 1. Nitrogen dioxide and cyclohexane are added in a circulating reactor to form an oxidation solution, and the mass percentage concentration of nitrogen dioxide in the oxidation solution is 5% to 75%, and then add regenerated cellulose to completely soak the regenerated cellulose in the oxidation solution, seal the reactor, and react at 5 to 45°C for 1 to 72 hours to obtain the oxidation product; 2. Use cyclohexane Rinse the oxidized product 2 to 5 times, then use an aqueous ethanol solution with a volume concentration of 20% to 95% to wash the oxidized product 2 to 3 times, and then use absolute ethanol to rinse the oxidized product 3 to 5 times; 3. Then rinse the oxidized product with absolute ethanol The final oxidized product is freeze-dried at -80～-10°C, and the drying time is 24～72 hours, and the oxidized regenerated cellulose absorbable hemostatic material is obtained; the mass ratio of regenerated cellulose to nitrogen dioxide in the oxidizing solution in step 1 is 0.01 to 100:1.
本发明选用环己烷(C6H12)作为二氧化氮溶剂，使二氧化氮发挥较高的氧化效率(与传统溶剂CCl4、CFCs、PFCs相当)，同时解决了环境污染、气候影响问题，而且本方法反应过程容易控制，适于产业化并以较低成本制备出氧化再生纤维素医用可吸收止血材料。The present invention selects cyclohexane (C 6 H 12 ) as the nitrogen dioxide solvent, so that the nitrogen dioxide can exert a higher oxidation efficiency (equal to the traditional solvents CCl 4 , CFCs, PFCs), and at the same time solves the problems of environmental pollution and climate impact , and the reaction process of the method is easy to control, suitable for industrialization, and can prepare oxidized regenerated cellulose medical absorbable hemostatic material at relatively low cost.
附图说明 Description of drawings
图1为具体实施方式十一和十二中环己烷和四氯化碳溶剂体系制备的氧化再生纤维素的红外曲线；图2为具体实施方式十一和十二中环己烷和四氯化碳溶剂体系制备的氧化再生纤维素的固态13C核磁曲线。Fig. 1 is the infrared curve of the oxidized regenerated cellulose prepared by cyclohexane and carbon tetrachloride solvent system in specific embodiment eleven and twelve; Fig. 2 is cyclohexane and carbon tetrachloride in specific embodiment eleven and twelve Solid state 13 C NMR curves of oxidized regenerated cellulose prepared in solvent system.
具体实施方式 Detailed ways
本发明技术方案不局限于以下所列举具体实施方式，还包括各具体实施方式间的任意组合。The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.
具体实施方式一：本实施方式氧化再生纤维素可吸收止血材料的制备方法，按以下步骤进行：一、将二氧化氮和环己烷加入到循环反应器中，形成氧化液，氧化液中二氧化氮的质量百分比浓度为5％～75％，然后再加入再生纤维素，使再生纤维素完全浸泡在氧化液中，密封反应器，于5～45℃反应时间1～72h，得氧化产物；二、用环己烷冲洗氧化产物2～5次，然后使用体积浓度为20％～95％的乙醇水溶液冲洗氧化产物2～3次，再用无水乙醇冲洗氧化产物3～5次；三、然后将无水乙醇冲洗后的氧化产物置于-80～-10℃冷冻干燥，干燥时间为24～72h，即得到氧化再生纤维素可吸收止血材料；其中步骤一中再生纤维素与氧化液中二氧化氮的质量比为0.01～100∶1。Specific Embodiment 1: The preparation method of the oxidized regenerated cellulose absorbable hemostatic material in this embodiment is carried out according to the following steps: 1. Nitrogen dioxide and cyclohexane are added to the circulating reactor to form an oxidizing liquid, and two in the oxidizing liquid The mass percent concentration of nitrogen oxide is 5% to 75%, and then regenerated cellulose is added to completely soak the regenerated cellulose in the oxidation solution, the reactor is sealed, and the reaction time is 1 to 72 hours at 5 to 45°C to obtain the oxidation product; 2. Rinse the oxidized product with cyclohexane for 2 to 5 times, then use an aqueous ethanol solution with a volume concentration of 20% to 95% to rinse the oxidized product 2 to 3 times, and then rinse the oxidized product with absolute ethanol for 3 to 5 times; 3. Then put the oxidized product rinsed with absolute ethanol at -80～-10℃ to freeze-dry for 24～72 hours to obtain the oxidized regenerated cellulose absorbable hemostatic material; wherein the regenerated cellulose is mixed with the oxidized solution in step 1 The mass ratio of nitrogen dioxide is 0.01-100:1.
本实施方式步骤一所述再生纤维素可以为粉末状、短丝状、长丝状或织物状。The regenerated cellulose in Step 1 of this embodiment may be in the form of powder, short filament, filament or fabric.
步骤一反应过程中的氧化液持续循环，使之与再生纤维素充分接触。The oxidation solution in the reaction process of step 1 is continuously circulated to make it fully contact with the regenerated cellulose.
具体实施方式二：本实施方式与具体实施方式一不同的是：步骤一氧化液中二氧化氮的质量百分比浓度为20％～50％。其它与具体实施方式一相同。Embodiment 2: The difference between this embodiment and Embodiment 1 is that the concentration of nitrogen dioxide in the oxidation solution in step 1 is 20%-50% by mass. Others are the same as in the first embodiment.
具体实施方式三：本实施方式与具体实施方式一或二不同的是：步骤一中再生纤维素的聚合度为100～500。其它与具体实施方式一或二相同。Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is that the degree of polymerization of the regenerated cellulose in step 1 is 100-500. Others are the same as in the first or second embodiment.
具体实施方式四：本实施方式与具体实施方式一至三之一不同的是：步骤一中再生纤维素与氧化液中二氧化氮的质量比为5～90∶1。其它与具体实施方式一至三之一相同。Embodiment 4: This embodiment differs from Embodiments 1 to 3 in that the mass ratio of regenerated cellulose to nitrogen dioxide in the oxidizing solution in step 1 is 5-90:1. Others are the same as those in the first to third specific embodiments.
具体实施方式五：本实施方式与具体实施方式一至三之一不同的是：步骤一中再生纤维素与氧化液中二氧化氮的质量比为20～70∶1。其它与具体实施方式一至三之一相同。Embodiment 5: This embodiment differs from Embodiment 1 to Embodiment 3 in that: in step 1, the mass ratio of regenerated cellulose to nitrogen dioxide in the oxidizing solution is 20-70:1. Others are the same as those in the first to third specific embodiments.
具体实施方式六：本实施方式与具体实施方式一至五之一不同的是：步骤一于10～40℃反应时间10～60h。其它与具体实施方式一至五之一相同。Embodiment 6: This embodiment is different from Embodiment 1 to Embodiment 5 in that: Step 1 is carried out at 10-40° C. for 10-60 hours. Others are the same as one of the specific embodiments 1 to 5.
具体实施方式七：本实施方式与具体实施方式一至五之一不同的是：步骤一于20～30℃反应时间30～40h。其它与具体实施方式一至五之一相同。Embodiment 7: The difference between this embodiment and one of Embodiments 1 to 5 is that the reaction time of Step 1 is 30-40 hours at 20-30°C. Others are the same as one of the specific embodiments 1 to 5.
具体实施方式八：本实施方式与具体实施方式一至七之一不同的是：步骤二中使用体积浓度为40％～70％的乙醇水溶液冲洗氧化产物3次。其它与具体实施方式一至七之一相同。Embodiment 8: This embodiment differs from Embodiment 1 to Embodiment 7 in that: in step 2, an aqueous ethanol solution with a volume concentration of 40% to 70% is used to wash the oxidation product 3 times. Others are the same as one of the specific embodiments 1 to 7.
具体实施方式九：本实施方式与具体实施方式一至八之一不同的是：步骤三中将无水乙醇冲洗后的氧化产物置于-50～-30℃冷冻干燥。其它与具体实施方式一至八之一相同。Embodiment 9: This embodiment differs from Embodiments 1 to 8 in that: in step 3, the oxidation product washed with absolute ethanol is placed at -50 to -30° C. for freeze-drying. Others are the same as one of the specific embodiments 1 to 8.
具体实施方式十：本实施方式与具体实施方式一至九之一不同的是：步骤三中干燥时间为30～50h。其它与具体实施方式一至九之一相同。Embodiment 10: This embodiment is different from Embodiment 1 to Embodiment 9 in that: the drying time in step 3 is 30-50 hours. Others are the same as one of the specific embodiments 1 to 9.
具体实施方式十一：本实施方式氧化再生纤维素可吸收止血材料的制备方法，按以下步骤进行：一、将40g二氧化氮和160g环己烷加入到循环反应器中，形成氧化液，然后再加入8.0g再生纤维素，使再生纤维素完全浸泡在氧化液中，密封反应器，于19℃反应时间24h，得氧化产物；二、用环己烷冲洗氧化产物3次，然后使用体积浓度为80％的乙醇水溶液冲洗氧化产物3次，再用无水乙醇冲洗氧化产物5次；三、然后将无水乙醇冲洗后的氧化产物置于-50℃冷冻干燥，干燥时间为48h，即得到氧化再生纤维素可吸收止血材料。Embodiment 11: The preparation method of oxidized regenerated cellulose absorbable hemostatic material in this embodiment is carried out according to the following steps: 1. Add 40g of nitrogen dioxide and 160g of cyclohexane into a circulating reactor to form an oxidation solution, and then Then add 8.0g of regenerated cellulose to completely soak the regenerated cellulose in the oxidizing solution, seal the reactor, and react at 19°C for 24 hours to obtain the oxidized product; Rinse the oxidized product with 80% ethanol aqueous solution for 3 times, and then wash the oxidized product with absolute ethanol for 5 times; 3. Then freeze-dry the oxidized product after rinsing with absolute ethanol at -50°C for 48 hours to obtain Oxidized regenerated cellulose absorbs hemostatic material.
本实施方式步骤一所述再生纤维素为长丝状。The regenerated cellulose described in Step 1 of this embodiment is in the form of filaments.
步骤一反应过程中的氧化液持续循环，使之与再生纤维素充分接触。The oxidation solution in the reaction process of step 1 is continuously circulated to make it fully contact with the regenerated cellulose.
本实施方式制备的氧化再生纤维素羧基含量为16.23％，红外曲线见图1中B曲线，固态13C核磁曲线见图2中B曲线。The carboxyl content of the oxidized regenerated cellulose prepared in this embodiment is 16.23%. The infrared curve is shown in curve B in FIG. 1 , and the solid-state 13 C NMR curve is shown in curve B in FIG. 2 .
对比实验：将环己烷改为四氯化碳，其他与本实施方式相同。制得的氧化再生纤维素羧基含量为16.58％，红外曲线见图1中D曲线，固态13C核磁曲线见图2中D曲线。Comparative experiment: change cyclohexane to carbon tetrachloride, and the others are the same as this embodiment. The obtained oxidized regenerated cellulose has a carboxyl content of 16.58%. The infrared curve is shown in the curve D in FIG. 1 , and the solid state 13 C NMR curve is shown in the curve D in FIG. 2 .
具体实施方式十二：本实施方式氧化再生纤维素可吸收止血材料的制备方法，按以下步骤进行：一、将40g二氧化氮和160g环己烷加入到循环反应器中，形成氧化液，然后再加入8.0g再生纤维素，使再生纤维素完全浸泡在氧化液中，密封反应器，于19℃反应时间48h，得氧化产物；二、用环己烷冲洗氧化产物3次，然后使用体积浓度为80％的乙醇水溶液冲洗氧化产物3次，再用无水乙醇冲洗氧化产物5次；三、然后将无水乙醇冲洗后的氧化产物置于-50℃冷冻干燥，干燥时间为48h，即得到氧化再生纤维素可吸收止血材料。Embodiment 12: The preparation method of the oxidized regenerated cellulose absorbable hemostatic material in this embodiment is carried out according to the following steps: 1. Add 40 g of nitrogen dioxide and 160 g of cyclohexane into a circulating reactor to form an oxidation solution, and then Then add 8.0g of regenerated cellulose to completely soak the regenerated cellulose in the oxidizing solution, seal the reactor, and react at 19°C for 48 hours to obtain the oxidized product; Rinse the oxidized product with 80% ethanol aqueous solution for 3 times, and then wash the oxidized product with absolute ethanol for 5 times; 3. Then freeze-dry the oxidized product after rinsing with absolute ethanol at -50°C for 48 hours to obtain Oxidized regenerated cellulose absorbs hemostatic material.
本实施方式步骤一所述再生纤维素为织物状。The regenerated cellulose described in Step 1 of this embodiment is in the form of fabric.
步骤一反应过程中的氧化液持续循环，使之与再生纤维素充分接触。The oxidation solution in the reaction process of step 1 is continuously circulated to make it fully contact with the regenerated cellulose.
本实施方式制备的氧化再生纤维素素羧基含量为18.32％，红外曲线见图1中C曲线，固态13C核磁曲线见图2中C曲线。The carboxyl content of the oxidized regenerated cellulose prepared in this embodiment is 18.32%. The infrared curve is shown in curve C in FIG. 1 , and the solid-state 13 C NMR curve is shown in curve C in FIG. 2 .
对比实验：将环己烷改为四氯化碳，其他与本实施方式相同。制得的氧化再生纤维素羧基含量为18.41％，红外曲线见图1中E曲线，固态13C核磁曲线见图2中E曲线。Comparative experiment: change cyclohexane to carbon tetrachloride, and the others are the same as this embodiment. The obtained oxidized regenerated cellulose has a carboxyl content of 18.41%. The infrared curve is shown in curve E in FIG. 1 , and the solid-state 13 C NMR curve is shown in curve E in FIG. 2 .
图1中A曲线为原料再生纤维素的红外曲线。由图1可见，环己烷(C6H12)溶剂体系制备的氧化再生纤维素的红外曲线(B、C)与四氯化碳(CCl4)溶剂体系制备的氧化再生纤维素的红外曲线上的特征吸收峰的峰位都基本相同。Curve A in Fig. 1 is the infrared curve of raw material regenerated cellulose. It can be seen from Figure 1 that the infrared curves of oxidized regenerated cellulose prepared in cyclohexane (C 6 H 12 ) solvent system (B, C) and the infrared curves of oxidized regenerated cellulose prepared in carbon tetrachloride (CCl 4 ) solvent system The peak positions of the characteristic absorption peaks are basically the same.
图2中A曲线为原料再生纤维素的固态13C核磁曲线。从图2可以看出，环己烷(C6H12)溶剂体系制备的氧化再生纤维素的固态13C核磁曲线(B、C)与四氯化碳(CCl4)溶剂体系制备的氧化再生纤维素的固态13C核磁曲线上的特征峰的峰位都相同。Curve A in Fig. 2 is the solid-state 13 C NMR curve of the raw material regenerated cellulose. It can be seen from Figure 2 that the solid-state 13 C NMR curves (B, C) of the oxidized regenerated cellulose prepared in the cyclohexane (C 6 H 12 ) solvent system and the oxidized regenerated cellulose prepared in the carbon tetrachloride (CCl 4 ) solvent system The peak positions of the characteristic peaks on the solid-state 13 C NMR curve of cellulose are all the same.
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