技术领域technical field
本发明属于生物质功能性高分子材料领域，具体涉及一种纳米纤维素/海藻酸钠导电水凝胶的制备方法。The invention belongs to the field of biomass functional polymer materials, and in particular relates to a preparation method of nanocellulose/sodium alginate conductive hydrogel.
背景技术Background technique
导电水凝胶不仅具备了传统水凝胶独特的物理化学特性，还结合了导电高分子优异的电学和光学性能，作为一种功能性水凝胶，在保持尺寸稳定性的前提下，可以通过调控导电高分子的类别和含量，使其具有不同的电导率，因而有望应用于生物医药、组织工程材料、生物传感器和生物燃料贮存元件等领域。近年来，采用无毒无害、具有良好生物相容性同时具备较多活性基团的天然多糖高聚物来制备导电水凝胶已成为研究热点。Conductive hydrogel not only possesses the unique physical and chemical properties of traditional hydrogels, but also combines the excellent electrical and optical properties of conductive polymers. As a functional hydrogel, it can pass Regulating the type and content of conductive polymers makes them have different conductivity, so it is expected to be applied in the fields of biomedicine, tissue engineering materials, biosensors and biofuel storage components. In recent years, the use of non-toxic, harmless, good biocompatibility and natural polysaccharide polymers with more active groups to prepare conductive hydrogels has become a research hotspot.
海藻酸钠是一种无毒、无刺激、无溶血效应，具有良好的生物相容性和生物可降解特性的天然多糖高聚物，海藻酸钠结构中含有大量的-COO-基团，在金属阳离子存在的情况下，易与其发生离子交联形成网络结构，从而形成水凝胶。纳米纤维素是一种具有优异力学性能、质轻、高比表面积、可再生、可生物降解等特性的新型纳米材料。纳米纤维素表面含有大量的羟基，可通过氢键作用力自组装形成具有一定柔韧性的三维网络结构的基体材料。将纳米纤维素运用于多糖高聚合物中，可与聚合物形成三维空间网络结构，赋予材料较好的力学强度，改善了单一组分聚合物材料存在性能不佳，强度低、易变形等缺点，同时由于纳米纤维素自身也是天然原料的优势，其废弃物也可生物降解。将纳米纤维素羧基化后，添加到海藻酸钠体系中，通过阳离子交联形成具有三维网络结构的水凝胶，在水凝胶上原位聚合吡咯可得到一种基于阳离子交联的纳米纤维素/海藻酸钠导电水凝胶。该导电水凝胶具有较高的机械强度，在导电材料和生物医用领域具有一定的潜在应用价值。Sodium alginate is a non-toxic, non-irritating, non-hemolytic effect, natural polysaccharide polymer with good biocompatibility and biodegradability. The structure of sodium alginate contains a large number of -COO- groups. In the presence of metal cations, it is easy to undergo ionic cross-linking with them to form a network structure, thereby forming a hydrogel. Nanocellulose is a new type of nanomaterial with excellent mechanical properties, light weight, high specific surface area, renewable and biodegradable properties. The surface of nanocellulose contains a large number of hydroxyl groups, which can self-assemble through hydrogen bonding forces to form a matrix material with a certain degree of flexibility and a three-dimensional network structure. The application of nanocellulose in high polysaccharide polymers can form a three-dimensional space network structure with the polymer, endow the material with better mechanical strength, and improve the shortcomings of single-component polymer materials such as poor performance, low strength, and easy deformation. At the same time, due to the advantage that nanocellulose itself is also a natural raw material, its waste is also biodegradable. After the nanocellulose is carboxylated, it is added to the sodium alginate system to form a hydrogel with a three-dimensional network structure through cationic crosslinking, and a nanofiber based on cationic crosslinking can be obtained by in situ polymerizing pyrrole on the hydrogel Alginate/sodium alginate conductive hydrogel. The conductive hydrogel has high mechanical strength and has certain potential application value in the field of conductive materials and biomedicine.
发明内容Contents of the invention
本发明的目的在于针对现有技术不足，提供一种纳米纤维素/海藻酸钠导电水凝胶的制备方法。本发明制得的水凝胶具有稳定的尺寸结构和三维网络结构，具有良好的机械性能和导电性，其电导率可达10-3～10-2 S/cm，压缩强度可达0.5～0.9 MPa，储能模量和损耗模量分别可达103～104 Pa、102～103 Pa。The object of the present invention is to provide a preparation method of nanocellulose/sodium alginate conductive hydrogel to solve the deficiencies of the prior art. The hydrogel prepared by the present invention has a stable size structure and a three-dimensional network structure, and has good mechanical properties and electrical conductivity. Its electrical conductivity can reach 10-3 to 10-2 S/cm, and its compressive strength can reach 0.5 to 0.9 MPa, storage modulus and loss modulus can reach 103 ~ 104 Pa, 102 ~ 103 Pa, respectively.
为实现上述目的，本发明采用如下技术方案：To achieve the above object, the present invention adopts the following technical solutions:
一种纳米纤维素/海藻酸钠导电水凝胶的制备方法，具体包括以下步骤：A preparation method of nanocellulose/sodium alginate conductive hydrogel, specifically comprising the following steps:
（1）将纤维原料加入到硫酸溶液中，经超声处理制备得到纳米纤维素，经冷冻干燥后得到纳米纤维素粉末；(1) Add fiber raw materials into sulfuric acid solution, prepare nanocellulose by ultrasonic treatment, and obtain nanocellulose powder after freeze-drying;
（2）将纳米纤维素粉末加入含有四甲基哌啶氮氧化物（TEMPO）、NaBr和NaClO的水溶液中，在25℃下反应6小时；反应结束后，用蒸馏水离心洗涤3~5次后收集C6位羧基化的纳米纤维，冷冻干燥得到羧基化纳米纤维素粉末；(2) Add nanocellulose powder into an aqueous solution containing tetramethylpiperidine nitrogen oxide (TEMPO), NaBr and NaClO, and react at 25°C for 6 hours; after the reaction, wash with distilled water for 3 to 5 times collecting nanofibers carboxylated at the C6 position, and freeze-drying to obtain carboxylated nanocellulose powder;
（3）取步骤（2）中得到的羧基化纳米纤维素粉末和海藻酸钠粉末于圆底烧瓶中，加入一定量的蒸馏水得到总浓度为10wt%的纳米纤维素/海藻酸钠混合溶液，在800W超声条件下搅拌分散2小时形成纳米纤维素/海藻酸钠悬浊液；将纳米纤维素/海藻酸钠悬浊液倒入成型模具中，随后浸泡于质量分数为5%的阳离子水溶液中24小时，在此期间，阳离子诱导羧基化纳米纤维素和海藻酸钠交联，形成阳离子交联并具有一定强度的纳米纤维素/海藻酸钠水凝胶；(3) Take the carboxylated nanocellulose powder and sodium alginate powder obtained in step (2) in a round bottom flask, add a certain amount of distilled water to obtain a mixed solution of nanocellulose/sodium alginate with a total concentration of 10wt%, Stir and disperse under 800W ultrasonic conditions for 2 hours to form a nanocellulose/sodium alginate suspension; pour the nanocellulose/sodium alginate suspension into a molding mold, and then soak in a cationic aqueous solution with a mass fraction of 5% 24 hours, during this period, cations induce carboxylated nanocellulose and sodium alginate to cross-link to form a cationic cross-linked nanocellulose/sodium alginate hydrogel with a certain strength;
（4）将步骤（3）中得到的阳离子交联的纳米纤维素/海藻酸钠水凝胶浸泡在浓度为1mol/L的FeCl3水溶液中，浸泡24小时，随后将水凝胶转移浸泡在浓度为0.5 mol/L的吡咯水溶液中，用0.1 mol/L的盐酸溶液调节pH=6.0，在4℃环境下反应12小时，用蒸馏水洗涤3~5次制得所述纳米纤维素/海藻酸钠导电水凝胶。(4) Soak the cationic cross-linked nanocellulose/sodium alginate hydrogel obtained in step (3) in 1mol/LFeCl3 aqueous solution for 24 hours, then transfer and soak the hydrogel in In the pyrrole aqueous solution with a concentration of 0.5 mol/L, adjust the pH=6.0 with 0.1 mol/L hydrochloric acid solution, react at 4°C for 12 hours, and wash with distilled water for 3 to 5 times to obtain the nanocellulose/alginic acid Sodium Conductive Hydrogels.
步骤（1）中所述的纤维原料为竹浆纤维、草浆纤维、微晶纤维素、纸浆纤维和棉纤维中的一种。The fiber raw material described in the step (1) is one of bamboo pulp fiber, straw pulp fiber, microcrystalline cellulose, pulp fiber and cotton fiber.
步骤（1）中所述的纤维原料与硫酸溶液的质量比为1:50。The mass ratio of the fiber raw material to the sulfuric acid solution in step (1) is 1:50.
步骤（1）中所述的硫酸溶液的质量浓度为50~65%。The mass concentration of the sulfuric acid solution described in step (1) is 50-65%.
步骤（1）中所述的超声处理的工艺参数为：超声温度为65℃，超声处理时间为3h。The process parameters of the ultrasonic treatment described in step (1) are: the ultrasonic temperature is 65° C., and the ultrasonic treatment time is 3 hours.
步骤（3）中所述的羧基化纳米纤维素粉末和海藻酸钠粉末的质量比为1:9~1:1。The mass ratio of carboxylated nanocellulose powder and sodium alginate powder in step (3) is 1:9-1:1.
步骤（3）中所述的阳离子为非一价阳离子，包括Ca2+、Cu2+、Ba2+、Sr2+，Al3+和Tb3+。The cations mentioned in step (3) are non-monovalent cations, including Ca2+ , Cu2+ , Ba2+ , Sr2+ , Al3+ and Tb3+ .
本发明的有益效果在于：The beneficial effects of the present invention are:
本发明利用无毒无害，具有良好生物相容性的天然高分子来制备导电水凝胶，将羧基化纳米纤维素添加到海藻酸钠体系中，通过阳离子交联得到具有三维网络结构的水凝胶后，在水凝胶上原位聚合吡咯，制备得到新型生物质基导电水凝胶。该水凝胶具有稳定的尺寸结构和三维网络结构，具有良好的机械性能和导电性，其电导率可达10-3～10-2 S/cm，压缩强度可达0.5～0.9 MPa，储能模量和损耗模量分别可达103～104 Pa、102～103 Pa，可更好的运用于生物医药和组织工程材料领域。The invention utilizes non-toxic, harmless, and natural polymers with good biocompatibility to prepare conductive hydrogels, adds carboxylated nano-cellulose to the sodium alginate system, and obtains water gels with a three-dimensional network structure through cationic cross-linking. After gelation, pyrrole was polymerized in situ on the hydrogel to prepare a new type of biomass-based conductive hydrogel. The hydrogel has a stable size structure and three-dimensional network structure, and has good mechanical properties and electrical conductivity. Its electrical conductivity can reach 10-3 ~ 10-2 S/cm, and its compressive strength can reach 0.5 ~ 0.9 MPa. The modulus and loss modulus can reach 103 -104 Pa and 102 -103 Pa respectively, which can be better used in the fields of biomedicine and tissue engineering materials.
具体实施方式Detailed ways
以下结合具体实施例对本发明做进一步说明，但本发明不仅仅限于这些实施例。The present invention will be further described below in conjunction with specific examples, but the present invention is not limited to these examples.
实施例1Example 1
（1）按料液比为1:50，将草浆纤维原料加入到50wt%硫酸溶液中，在65℃条件下超声3h制备得到纳米纤维素，经冷冻干燥后得到纳米纤维素粉末；(1) According to the material-to-liquid ratio of 1:50, the straw pulp fiber raw material was added to 50wt% sulfuric acid solution, and nanocellulose was prepared by ultrasonication at 65°C for 3 hours, and nanocellulose powder was obtained after freeze-drying;
（2）将10 g纳米纤维素粉末加入1000 ml含有0.16 g TEMPO（四甲基哌啶氮氧化物）、1.0 g NaBr和1.2 g NaClO的水溶液中，在25℃下反应6小时，反应结束后，用蒸馏水离心洗涤3次后收集C6位羧基化的纳米纤维，冷冻干燥得到羧基化纳米纤维素粉末；(2) Add 10 g of nanocellulose powder to 1000 ml of an aqueous solution containing 0.16 g of TEMPO (tetramethylpiperidine nitrogen oxide), 1.0 g of NaBr and 1.2 g of NaClO, and react at 25°C for 6 hours. After the reaction , after centrifuging and washing with distilled water for 3 times, the carboxylated nanofibers at the C6 position were collected, and freeze-dried to obtain carboxylated nanocellulose powder;
（3）取步骤（2）中得到的羧基化纳米纤维素粉末和海藻酸钠粉末于圆底烧瓶中，两者质量比为1:9，加入一定量的蒸馏水得到总浓度为10wt%的纳米纤维素/海藻酸钠混合溶液，在800W超声条件下搅拌分散2小时形成纳米纤维素海藻酸钠悬浊液；将此悬浊液倒入成型模具中，随后浸泡于质量分数为5%的Ca2+离子水溶液中24小时，在此期间，阳离子诱导羧基化纳米纤维素和海藻酸钠交联，形成阳离子交联并具有一定强度的纳米纤维素/海藻酸钠水凝胶；(3) Take the carboxylated nanocellulose powder and sodium alginate powder obtained in step (2) in a round bottom flask, the mass ratio of the two is 1:9, add a certain amount of distilled water to obtain a total concentration of 10wt% nano The cellulose/sodium alginate mixed solution was stirred and dispersed under 800W ultrasonic conditions for 2 hours to form a nano-cellulose sodium alginate suspension; the suspension was poured into a molding mold, and then soaked in Ca with a mass fraction of 5%.2+ in ionic aqueous solution for 24 hours, during this period, cations induce carboxylated nanocellulose and sodium alginate to crosslink to form a cationic crosslinked nanocellulose/sodium alginate hydrogel with a certain strength;
（4）将步骤（3）中阳离子交联的纳米纤维素/海藻酸钠水凝胶浸泡在浓度为1 mol/L的FeCl3水溶液中，浸泡24小时，随后将水凝胶转移浸泡在浓度为0.5 mol/L 的吡咯水溶液中，用0.1 mol/L 的盐酸溶液调节pH=6.0，在4℃环境下反应12小时，用蒸馏水洗涤3次即可得到导电水凝胶，即纳米纤维素/海藻酸钠导电水凝胶。(4) Soak the cationic cross-linked nanocellulose/sodium alginate hydrogel in step (3) in FeCl3 aqueous solution with a concentration of 1 mol/L for 24 hours, and then transfer and soak the hydrogel at a concentration of In the 0.5 mol/L pyrrole aqueous solution, adjust the pH=6.0 with 0.1 mol/L hydrochloric acid solution, react at 4°C for 12 hours, and wash with distilled water for 3 times to obtain the conductive hydrogel, that is, nanocellulose/ Sodium alginate conductive hydrogel.
实施例2Example 2
（1）按料液比为1:50，将纸浆纤维原料加入到55wt%硫酸溶液中，在65℃条件下超声3h制备得到纳米纤维素，经冷冻干燥后得到纳米纤维素粉末；(1) According to the material-to-liquid ratio of 1:50, the pulp fiber raw material was added to 55wt% sulfuric acid solution, and nanocellulose was prepared by ultrasonication at 65°C for 3 hours, and nanocellulose powder was obtained after freeze-drying;
（2）将10 g纳米纤维素粉末加入1000 ml含有0.16 g TEMPO（四甲基哌啶氮氧化物）、1.0 g NaBr和1.2 g NaClO的水溶液中，在25℃下反应6小时，反应结束后，用蒸馏水离心洗涤5次后收集C6位羧基化的纳米纤维，冷冻干燥得到羧基化纳米纤维素粉末；(2) Add 10 g of nanocellulose powder to 1000 ml of an aqueous solution containing 0.16 g of TEMPO (tetramethylpiperidine nitrogen oxide), 1.0 g of NaBr and 1.2 g of NaClO, and react at 25°C for 6 hours. After the reaction , using distilled water to centrifuge and wash 5 times, collect the nanofibers carboxylated at the C6 position, and freeze-dry to obtain carboxylated nanocellulose powder;
（3）取步骤（2）中得到的羧基化纳米纤维素粉末和海藻酸钠粉末于圆底烧瓶中，两者质量比为2:8，加入一定量的蒸馏水得到总浓度为10wt%的纳米纤维素/海藻酸钠混合溶液，在800W超声条件下搅拌分散2小时形成纳米纤维素海藻酸钠悬浊液；将此悬浊液倒入成型模具中，随后浸泡于质量分数为5%的Cu2+离子水溶液中24小时，在此期间，阳离子诱导羧基化纳米纤维素和海藻酸钠交联，形成阳离子交联并具有一定强度的纳米纤维素/海藻酸钠水凝胶；(3) Take the carboxylated nanocellulose powder and sodium alginate powder obtained in step (2) in a round bottom flask, the mass ratio of the two is 2:8, add a certain amount of distilled water to obtain a total concentration of 10wt% nano The cellulose/sodium alginate mixed solution was stirred and dispersed under 800W ultrasonic conditions for 2 hours to form a suspension of nano-cellulose sodium alginate; the suspension was poured into a molding mold, and then soaked in Cu with a mass fraction of 5%.2+ in ionic aqueous solution for 24 hours, during this period, cations induce carboxylated nanocellulose and sodium alginate to crosslink to form a cationic crosslinked nanocellulose/sodium alginate hydrogel with a certain strength;
（4）将步骤（3）中阳离子交联的纳米纤维素/海藻酸钠水凝胶浸泡在浓度为1 mol/L的FeCl3水溶液中，浸泡24小时，随后将水凝胶转移浸泡在浓度为0.5 mol/L 的吡咯水溶液中，用0.1 mol/L 的盐酸溶液调节pH=6.0，在4℃环境下反应12小时，用蒸馏水洗涤5次即可得到导电水凝胶，即纳米纤维素/海藻酸钠导电水凝胶。(4) Soak the cationic cross-linked nanocellulose/sodium alginate hydrogel in step (3) in FeCl3 aqueous solution with a concentration of 1 mol/L for 24 hours, and then transfer and soak the hydrogel at a concentration of In the 0.5 mol/L pyrrole aqueous solution, adjust the pH=6.0 with 0.1 mol/L hydrochloric acid solution, react at 4°C for 12 hours, and wash with distilled water for 5 times to obtain the conductive hydrogel, that is, nanocellulose/ Sodium alginate conductive hydrogel.
实施例3Example 3
（1）按料液比为1:50，将微晶纤维素原料加入到60wt%硫酸溶液中，在65℃条件下超声3h制备得到纳米纤维素，经冷冻干燥后得到纳米纤维素粉末；(1) According to the material-to-liquid ratio of 1:50, the microcrystalline cellulose raw material was added to 60wt% sulfuric acid solution, and nanocellulose was prepared by ultrasonication at 65°C for 3 hours, and nanocellulose powder was obtained after freeze-drying;
（2）将10 g纳米纤维素粉末加入1000 ml含有0.16 g TEMPO（四甲基哌啶氮氧化物）、1.0 g NaBr和1.2 g NaClO的水溶液中，在25℃下反应6小时，反应结束后，用蒸馏水离心洗涤3次后收集C6位羧基化的纳米纤维，冷冻干燥得到羧基化纳米纤维素粉末；(2) Add 10 g of nanocellulose powder to 1000 ml of an aqueous solution containing 0.16 g of TEMPO (tetramethylpiperidine nitrogen oxide), 1.0 g of NaBr and 1.2 g of NaClO, and react at 25°C for 6 hours. After the reaction , after centrifuging and washing with distilled water for 3 times, the carboxylated nanofibers at the C6 position were collected, and freeze-dried to obtain carboxylated nanocellulose powder;
（3）取步骤（2）中得到的羧基化纳米纤维素粉末和海藻酸钠粉末于圆底烧瓶中，两者质量比为3:7，加入一定量的蒸馏水得到总浓度为10wt%的纳米纤维素/海藻酸钠混合溶液，在800W超声条件下搅拌分散2小时形成纳米纤维素海藻酸钠悬浊液；将此悬浊液倒入成型模具中，随后浸泡于质量分数为5%的Ba2+离子水溶液中24小时，在此期间，阳离子诱导羧基化纳米纤维素和海藻酸钠交联，形成阳离子交联并具有一定强度的纳米纤维素/海藻酸钠水凝胶；(3) Take the carboxylated nanocellulose powder and sodium alginate powder obtained in step (2) in a round bottom flask, the mass ratio of the two is 3:7, add a certain amount of distilled water to obtain a total concentration of 10wt% nano The cellulose/sodium alginate mixed solution was stirred and dispersed under 800W ultrasonic conditions for 2 hours to form a nano-cellulose sodium alginate suspension; the suspension was poured into a molding mold, and then soaked in 5% Ba2+ in ionic aqueous solution for 24 hours, during this period, cations induce carboxylated nanocellulose and sodium alginate to crosslink to form a cationic crosslinked nanocellulose/sodium alginate hydrogel with a certain strength;
（4）将步骤（3）中阳离子交联的纳米纤维素/海藻酸钠水凝胶浸泡在浓度为1 mol/L的FeCl3水溶液中，浸泡24小时，随后将水凝胶转移浸泡在浓度为0.5 mol/L 的吡咯水溶液中，用0.1 mol/L 的盐酸溶液调节pH=6.0，在4℃环境下反应12小时，用蒸馏水洗涤3次即可得到导电水凝胶，即纳米纤维素/海藻酸钠导电水凝胶。(4) Soak the cationic cross-linked nanocellulose/sodium alginate hydrogel in step (3) in FeCl3 aqueous solution with a concentration of 1 mol/L for 24 hours, and then transfer and soak the hydrogel at a concentration of In the 0.5 mol/L pyrrole aqueous solution, adjust the pH=6.0 with 0.1 mol/L hydrochloric acid solution, react at 4°C for 12 hours, and wash with distilled water for 3 times to obtain the conductive hydrogel, that is, nanocellulose/ Sodium alginate conductive hydrogel.
实施例4Example 4
（1）按料液比为1:50，将棉花纤维原料加入到65wt%硫酸溶液中，在65℃条件下超声3h制备得到纳米纤维素，经冷冻干燥后得到纳米纤维素粉末；(1) According to the material-to-liquid ratio of 1:50, cotton fiber raw materials were added to 65wt% sulfuric acid solution, and nanocellulose was prepared by ultrasonication at 65°C for 3 hours, and nanocellulose powder was obtained after freeze-drying;
（2）将10 g纳米纤维素粉末加入1000 ml含有0.16 g TEMPO（四甲基哌啶氮氧化物）、1.0 g NaBr和1.2 g NaClO的水溶液中，在25℃下反应6小时，反应结束后，用蒸馏水离心洗涤4次后收集C6位羧基化的纳米纤维，冷冻干燥得到羧基化纳米纤维素粉末；(2) Add 10 g of nanocellulose powder to 1000 ml of an aqueous solution containing 0.16 g of TEMPO (tetramethylpiperidine nitrogen oxide), 1.0 g of NaBr and 1.2 g of NaClO, and react at 25°C for 6 hours. After the reaction , using distilled water to centrifuge and wash for 4 times, collect the nanofibers that are carboxylated at the C6 position, and freeze-dry to obtain carboxylated nanocellulose powder;
（3）取步骤（2）中得到的羧基化纳米纤维素粉末和海藻酸钠粉末于圆底烧瓶中，两者质量比为4:6，加入一定量的蒸馏水得到总浓度为10wt%的纳米纤维素/海藻酸钠混合溶液，在800W超声条件下搅拌分散2小时形成纳米纤维素海藻酸钠悬浊液；将此悬浊液倒入成型模具中，随后浸泡于质量分数为5%的Al3+离子水溶液中24小时，在此期间，阳离子诱导羧基化纳米纤维素和海藻酸钠交联，形成阳离子交联并具有一定强度的纳米纤维素/海藻酸钠水凝胶；(3) Take the carboxylated nanocellulose powder and sodium alginate powder obtained in step (2) in a round bottom flask, the mass ratio of the two is 4:6, add a certain amount of distilled water to obtain a total concentration of 10wt% nano The cellulose/sodium alginate mixed solution was stirred and dispersed under 800W ultrasonic conditions for 2 hours to form a nano-cellulose sodium alginate suspension; the suspension was poured into a molding mold, and then soaked in 5% Al3+ ionic aqueous solution for 24 hours, during this period, cations induce the crosslinking of carboxylated nanocellulose and sodium alginate to form a cationic crosslinked nanocellulose/sodium alginate hydrogel with a certain strength;
（4）将步骤（3）中阳离子交联的纳米纤维素/海藻酸钠水凝胶浸泡在浓度为1 mol/L的FeCl3水溶液中，浸泡24小时，随后将水凝胶转移浸泡在浓度为0.5 mol/L 的吡咯水溶液中，用0.1 mol/L 的盐酸溶液调节pH=6.0，在4℃环境下反应12小时，用蒸馏水洗涤4次即可得到导电水凝胶，即纳米纤维素/海藻酸钠导电水凝胶。(4) Soak the cationic cross-linked nanocellulose/sodium alginate hydrogel in step (3) in FeCl3 aqueous solution with a concentration of 1 mol/L for 24 hours, and then transfer and soak the hydrogel at a concentration of In the 0.5 mol/L pyrrole aqueous solution, adjust the pH=6.0 with 0.1 mol/L hydrochloric acid solution, react at 4°C for 12 hours, and wash 4 times with distilled water to obtain the conductive hydrogel, that is, nanocellulose/ Sodium alginate conductive hydrogel.
实施例5Example 5
（1）按料液比为1:50，将竹浆纤维原料加入到65wt%硫酸溶液中，在65℃条件下超声3h制备得到纳米纤维素，经冷冻干燥后得到纳米纤维素粉末；(1) According to the material-to-liquid ratio of 1:50, the bamboo pulp fiber raw material was added to 65wt% sulfuric acid solution, and nanocellulose was prepared by ultrasonication at 65°C for 3 hours, and nanocellulose powder was obtained after freeze-drying;
（2）将10 g纳米纤维素粉末加入1000 ml含有0.16 g TEMPO（四甲基哌啶氮氧化物）、1.0 g NaBr和1.2 g NaClO的水溶液中，在25℃下反应6小时，反应结束后，用蒸馏水离心洗涤4次后收集C6位羧基化的纳米纤维，冷冻干燥得到羧基化纳米纤维素粉末；(2) Add 10 g of nanocellulose powder to 1000 ml of an aqueous solution containing 0.16 g of TEMPO (tetramethylpiperidine nitrogen oxide), 1.0 g of NaBr and 1.2 g of NaClO, and react at 25°C for 6 hours. After the reaction , using distilled water to centrifuge and wash for 4 times, collect the nanofibers that are carboxylated at the C6 position, and freeze-dry to obtain carboxylated nanocellulose powder;
（3）取步骤（2）中得到的羧基化纳米纤维素粉末和海藻酸钠粉末于圆底烧瓶中，两者质量比为5:5，加入一定量的蒸馏水得到总浓度为10wt%的纳米纤维素/海藻酸钠混合溶液，在800W超声条件下搅拌分散2小时形成纳米纤维素海藻酸钠悬浊液；将此悬浊液倒入成型模具中，随后浸泡于质量分数为5%的Tb3+离子水溶液中24小时，在此期间，阳离子诱导羧基化纳米纤维素和海藻酸钠交联，形成阳离子交联并具有一定强度的纳米纤维素/海藻酸钠水凝胶；(3) Take the carboxylated nanocellulose powder and sodium alginate powder obtained in step (2) in a round bottom flask, the mass ratio of the two is 5:5, add a certain amount of distilled water to obtain a total concentration of 10wt% nano The cellulose/sodium alginate mixed solution was stirred and dispersed under 800W ultrasonic conditions for 2 hours to form a nano-cellulose sodium alginate suspension; the suspension was poured into a molding mold, and then soaked in 5% Tb3+ ionic aqueous solution for 24 hours, during this period, cations induce the crosslinking of carboxylated nanocellulose and sodium alginate to form a cationic crosslinked nanocellulose/sodium alginate hydrogel with a certain strength;
（4）将步骤（3）中阳离子交联的纳米纤维素/海藻酸钠水凝胶浸泡在浓度为1 mol/L的FeCl3水溶液中，浸泡24小时，随后将水凝胶转移浸泡在浓度为0.5 mol/L 的吡咯水溶液中，用0.1 mol/L 的盐酸溶液调节pH=6.0，在4℃环境下反应12小时，用蒸馏水洗涤4次即可得到导电水凝胶，即纳米纤维素/海藻酸钠导电水凝胶。(4) Soak the cationic cross-linked nanocellulose/sodium alginate hydrogel in step (3) in FeCl3 aqueous solution with a concentration of 1 mol/L for 24 hours, and then transfer and soak the hydrogel at a concentration of In the 0.5 mol/L pyrrole aqueous solution, adjust the pH=6.0 with 0.1 mol/L hydrochloric acid solution, react at 4°C for 12 hours, and wash 4 times with distilled water to obtain the conductive hydrogel, that is, nanocellulose/ Sodium alginate conductive hydrogel.
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。The above descriptions are only preferred embodiments of the present invention, and all equivalent changes and modifications made according to the scope of the patent application of the present invention shall fall within the scope of the present invention.
| Application Number | Priority Date | Filing Date | Title |
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| CN201810127434.6ACN108250463A (en) | 2018-02-08 | 2018-02-08 | A kind of preparation method of nano-cellulose/sodium alginate conductive hydrogel |
| Application Number | Priority Date | Filing Date | Title |
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| CN201810127434.6ACN108250463A (en) | 2018-02-08 | 2018-02-08 | A kind of preparation method of nano-cellulose/sodium alginate conductive hydrogel |
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