Polypyrrole nano-silver loaded nano-cellulose conductive seasoning as well as preparation method and application thereof

Abstract

The invention relates to the technical field of composite fibers, and particularly discloses a conductive polylactic acid polypyrrole nano-silver loaded nano-cellulose composite fiber and a preparation method thereof. The conductive polylactic acid polypyrrole nano-silver loaded nano-cellulose composite fiber is prepared from the following raw materials: a polypyrrole nano-silver loaded nano-cellulose conductive seasoning; the polypyrrole nano-silver loaded nano-cellulose conductive seasoning is prepared by the following steps: respectively preparing a nano-cellulose suspension, a phytic acid solution, a silver nitrate solution and a glucose solution; the preparation method comprises the following steps: mixing a nano-cellulose suspension and a phytic acid solution, stirring, adding a silver nitrate solution, stirring, adding a glucose solution, carrying out ultrasonic treatment, adding a pyrrole monomer, adding a dopant, and adding ferric trichloride hexahydrate under a stirring condition to prepare the polypyrrole nano-silver loaded nano-cellulose conductive seasoning. The maximum volume conductivity of the obtained composite fiber reaches 1.35 * 10 <-4 > S / cm, and the conductivity of the nanocellulose is improved.

Description

Technical Field

[0001] The present application relates to the field of composite fibers, and more specifically, to a polypyrrole nanosilver-loaded nanocellulose conductive seasoning, a preparation method thereof, and an application thereof. Background Art

[0002] Cellulose, a natural polymer, is mostly derived from cotton, wood, straw, and other materials. Its greatest advantage is its biodegradability and recyclability, making it widely used in industries such as papermaking, textiles, printing and dyeing, daily chemicals, construction, and coatings. However, cellulose's non-conductivity limits its application in electrical fields such as electromagnetic shielding, sensors, semiconductor devices, and antistatic treatment. Therefore, researchers are taking advantage of the abundant hydroxyl groups on the surface of cellulose molecular chains, which can be combined with other conductive materials to improve cellulose's conductivity. With the development of industrial technology, the research value of cellulose-based conductive composite materials is becoming increasingly important.

[0003] In related technologies, graphene, carbon black or metal powder is added to cellulose as a conductive material to improve the conductivity of cellulose. Although the cellulose has conductivity, the graphene reduces the continuity of the conductive network, resulting in low conductivity of the cellulose. Summary of the Invention

[0004] In order to improve the conductivity of nanocellulose, the present application provides a polypyrrole nanosilver loaded nanocellulose conductive seasoning and its preparation method and application.

[0005] In a first aspect, the present application provides a method for preparing a polypyrrole nanosilver-loaded nanocellulose conductive seasoning, which adopts the following technical solution: A method for preparing a polypyrrole nanosilver-loaded nanocellulose conductive seasoning comprises the following steps: S1. preparing a nanocellulose suspension with a mass fraction of 1-3%, a phytic acid solution with a mass fraction of 1%, a silver nitrate solution with a mass fraction of 6-8%, and a glucose solution with a mass fraction of 3-10% respectively; S2. First, the nanocellulose suspension is mixed with the phytic acid solution, stirred at 200-300 r / min for 0.5-2 h, then the silver nitrate solution is added, stirred at 500-1000 r / min for 0.5-1 h, and then the glucose solution is added, and ultrasonic treatment is performed to obtain a nanosilver-loaded nanocellulose suspension; S3. Adding a pyrrole monomer of the same mass as the nanosilver-loaded nanocellulose suspension to the nanosilver-loaded nanocellulose suspension, then adding a dopant of the same mass as the pyrrole monomer, and finally adding ferric chloride hexahydrate under stirring to prepare a polypyrrole nanosilver-loaded nanocellulose conductive seasoning.

[0006] The liquid medium for the nanocellulose suspension, phytic acid solution, silver nitrate solution, and glucose solution in this application is all water. The mass ratio of the nanocellulose suspension to the phytic acid solution is 1:(10-20); the mass ratio of the silver nitrate solution to the nanocellulose suspension is 1:(10-15); the mass ratio of the silver nitrate solution to the glucose solution is 1:(4-6); and the molar ratio of the pyrrole monomer to ferric chloride hexahydrate is 1:(1-3).

[0007] By adopting the above scheme, the nanocellulose suspension is mixed with a phytic acid solution and stirred at 200-300r / min for 0.5-2h to prevent the nanocellulose from agglomerating and ensure the uniformity of the suspension. In addition, phytic acid provides free hydrogen ions to form a proton conduction path with the nanocellulose network, thereby enhancing the stability of the nanocellulose suspension. Silver nitrate solution is added and stirred to obtain a phytic acid silver precipitate deposited on the surface of the cellulose nanocrystals. The silver ions are adsorbed by the hydroxyl groups of the nanocellulose and the phosphate groups of the phytic acid, uniformly dispersed in the composite system, forming uniformly distributed silver ion adsorption sites. Glucose solution is added to reduce the silver ions to nanosilver, and after ultrasonic treatment, a nanosilver-loaded nanocellulose suspension is obtained. Pyrrole monomers are then added to the nanosilver-loaded nanocellulose suspension to form polypyrroles with a conjugated π electron system. Nanosilver can enhance the conductive network of polypyrrole. On the other hand, nanosilver can promote the polymerization of pyrrole monomers, so that polypyrrole and nanosilver are composited to enhance the conductivity of the conductive seasoning. In addition, polypyrrole can be in situ polymerized on the nanosilver surface to form a core-shell structure, preventing nanosilver from oxidizing or agglomerating. Adding a dopant neutralizes the positive charge on the polypyrrole molecular chain, enhancing π electron delocalization and significantly improving conductivity. Furthermore, the dopant can fill the gaps between polypyrrole molecular chains, reducing environmental damage to the conductive chains. Adding ferric chloride hexahydrate triggers the polymerization of pyrrole to form polypyrrole. Furthermore, the chloride ions released by the dissociation of ferric chloride hexahydrate embed into the polypyrrole molecular chain, neutralizing the positive charge and enhancing the conductivity of the conductive seasoning.

[0008] Preferably, in step S2, the dopants are sodium bromide and sodium dodecylbenzenesulfonate, and sodium bromide and sodium dodecylbenzenesulfonate are added in an amount equal to that of the pyrrole monomer and the like.

[0009] By adopting the above scheme, sodium bromide and sodium dodecylbenzenesulfonate are selected as dopants. The addition of sodium bromide directly neutralizes the positive charge and enhances the delocalization of π electrons, which can improve the conductivity of the composite fiber and the stability of the system. Sodium bromide will compress the double layer, reduce electrostatic repulsion, and enhance the adsorption of pyrrole monomers at the interface.

[0010] The addition of sodium dodecylbenzenesulfonate can expand the distance between polypyrrole molecular chains, reduce the carrier transmission resistance, and improve the conductivity of the composite fiber; in addition, sodium dodecylbenzenesulfonate can stabilize nanosilver and polypyrrole particles through electrostatic repulsion to improve the conductivity of the composite fiber.

[0011] The sequential addition of sodium bromide and sodium dodecylbenzenesulfonate can synergistically regulate the equilibrium stability of the suspension and optimize the microstructure of the polypyrrole nanosilver-loaded nanocellulose conductive seasoning, thereby further improving the conductivity and flexibility of the composite fiber.

[0012] Preferably, the nanocellulose in the nanocellulose suspension is one or more of cellulose nanocrystals, cellulose nanowires, cellulose microwires and bacterial cellulose.

[0013] The nanocellulose in the raw material of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fiber of the present application is selected from one or more of cellulose nanocrystals, cellulose nanowires, cellulose microwires and bacterial cellulose. The performance of the composite fiber is predictable, and the conductivity and flexibility of the composite fiber can be guaranteed.

[0014] In a second aspect, the present application provides a conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fiber, which comprises the following raw materials: polylactic acid and a polypyrrole nanosilver loaded nanocellulose conductive seasoning prepared by the preparation method according to any one of claims 1-3.

[0015] In a third aspect, the present application provides a method for preparing any of the above-mentioned conductive polylactic acid-polypyrrole nanosilver-loaded nanocellulose composite fibers, which is specifically achieved through the following technical solutions: A method for preparing conductive polylactic acid-polypyrrole nanosilver-loaded nanocellulose composite fibers comprises the following steps: S1, melt-mixing a polypyrrole nanosilver-loaded nanocellulose conductive seasoning with polylactic acid to prepare a conductive masterbatch containing 10-15% by mass of the polypyrrole nanosilver-loaded nanocellulose conductive seasoning; S2. Weigh the conductive masterbatch and polylactic acid spinning melt, use a twin-screw extrusion system to control the melting and transportation of the conductive masterbatch and the polylactic acid spinning melt respectively, extrude the conductive masterbatch from the inner hole and extrude the polylactic acid spinning melt from the outer ring, and obtain a conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fiber with a skin-core structure in which the skin component is the conductive masterbatch and the polylactic acid spinning melt is the core component.

[0016] By adopting the above scheme, the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fiber is obtained, which combines the degradability of polylactic acid, the conductivity of polypyrrole, the further improvement of conductivity by nanosilver and the enhanced mechanical properties of nanocellulose, promotes the dispersion of nanosilver, improves the interface bonding characteristics of polylactic acid and polypyrrole, and gives the composite fiber excellent conductivity and mechanical properties.

[0017] Preferably, the mass ratio of the sheath component to the core component in step S2 is 1:(2-2.5).

[0018] The mass ratio of the sheath component to the core component in step S2 of the present application is any value within the range of 1:(2-2.5), and the performance of the composite fiber is predictable, and the conductivity and flexibility of the composite fiber can be guaranteed.

[0019] By adopting the above scheme, the mass ratio of the sheath component to the core component is adjusted, so that the thickness of the sheath component made of the conductive masterbatch is moderate and the coating is uniform, so as to further improve the mechanical properties and conductivity of the composite fiber.

[0020] Preferably, in step S1, inorganic particles are added when the polypyrrole nanosilver-loaded nanocellulose conductive seasoning and polylactic acid are melt-mixed; the mass ratio of the inorganic particles to the polylactic acid is 1:(3-7).

[0021] Preferably, the inorganic particles are carbon nanotubes.

[0022] By adopting the above scheme, carbon nanotubes have a high specific surface area and good dispersibility, which can promote the compatibility between polypyrrole nanosilver loaded nanocellulose conductive seasoning and melted polylactic acid, promote the formation of a conductive network, and improve the conductivity of the polypyrrole nanosilver loaded nanocellulose conductive seasoning; on the other hand, carbon nanotubes, as rigid particles, are evenly dispersed in polylactic acid, which can enhance the strength and toughness of the conductive masterbatch, that is, the skin component, effectively avoid cracking and peeling of the skin component, and improve the mechanical properties of the composite fiber.

[0023] Preferably, acetyl tributyl citrate is also added when adding carbon nanotubes in step S1; the mass ratio of acetyl tributyl citrate to carbon nanotubes is 1:(25-45).

[0024] By adopting the above scheme and adding acetyl tributyl citrate, the long-chain alkyl group in the acetyl tributyl citrate molecule can form a physical adsorption layer on the surface of the carbon nanotubes, produce a steric hindrance effect, hinder the agglomeration of the carbon nanotubes, further improve the dispersion of the carbon nanotubes, and thus further improve the conductivity and mechanical properties of the composite fiber.

[0025] In summary, this application includes at least one of the following beneficial technical effects: (1) The present invention controls the steps of preparing the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fiber to make the volume conductivity of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fiber 1.21×10 -4 S / cm, with high conductivity.

[0026] (2) In the present application, carbon nanotubes are added to the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers during the melt mixing of the polypyrrole nanosilver loaded nanocellulose conductive seasoning and polylactic acid in step S1, so that the volume conductivity of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers is 1.24×10 -4 S / cm, further improving the conductivity of nanocellulose.

[0027] (3) In the present application, when the conductive masterbatch is added to the polylactic acid and melt-mixed in step S1, carbon nanotubes and acetyl tributyl citrate are also added, and the ratio of the two is adjusted to make the volume conductivity of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fiber 1.27×10 -4 ~1.29×10 -4 S / cm, further improving the conductivity of nanocellulose. DETAILED DESCRIPTION

[0028] The following is a further detailed description of the present application in conjunction with specific examples. The following raw materials in this application are all commercially available products, and are intended to fully disclose the raw materials of this application, and should not be understood as limiting the source of the raw materials. Specifically: polylactic acid, with an active ingredient content of 99%; nanocellulose is selected from cellulose nanocrystals, with an active ingredient content of 99%, a width of 1-20nm, and a length of 200-800nm; phytic acid, with an active ingredient content of 99%; glucose, with an active ingredient content of 90%; pyrrole monomer, with an active ingredient content of 90%; sodium bromide and sodium dodecylbenzenesulfonate are selected as dopants, wherein the active ingredient content of sodium bromide and sodium dodecylbenzenesulfonate is 99%; ferric chloride hexahydrate, with an active ingredient content of 96%; nanohydroxyapatite, with a particle size of 20nm; carbon nanotubes, with a diameter of 2-4nm and a length of 5-15μm; acetyl tributyl citrate, with an active ingredient content of 99%; polylactic acid spinning melt, selected from NatureWorks Ingeo TM 6202D.

[0029] Example 1 The preparation method of the polypyrrole nanosilver loaded nanocellulose conductive seasoning of Example 1 comprises the following steps: S1. Prepare a 2% nanocellulose suspension, a 1% phytic acid solution, a 7% silver nitrate solution, and a 7% glucose solution respectively; S2. First, 1 kg of nanocellulose suspension was mixed with 15 kg of phytic acid solution, and the mixture was stirred at 250 r / min for 1.5 h. Then, 76.9 g of silver nitrate solution was added, and the mixture was stirred at 800 r / min for 0.8 h. Then, 384.6 g of glucose solution was added, and the mixture was ultrasonically treated to obtain a nanosilver-loaded nanocellulose suspension. S3. Add 1 kg of pyrrole monomer and 1.53 kg of sodium bromide (dopant) to 1 kg of nanosilver-loaded nanocellulose suspension, and finally add 8 kg of ferric chloride hexahydrate under stirring to prepare polypyrrole nanosilver-loaded nanocellulose conductive seasoning.

[0030] Example 2 The preparation method of the polypyrrole nanosilver-loaded nanocellulose conductive seasoning of Example 2 is the same as that of Example 1, except that step S3 is specifically as follows: 1 kg of pyrrole monomer is added to 1 kg of nanosilver-loaded nanocellulose suspension, and then 1.53 kg of sodium bromide and 5.19 kg of sodium dodecylbenzenesulfonate are added at the same time, and finally ferric chloride hexahydrate is added under stirring to obtain a polypyrrole nanosilver-loaded nanocellulose conductive seasoning. The remaining steps are the same as in Example 1.

[0031] Example 3 The preparation method of the polypyrrole nanosilver loaded nanocellulose conductive seasoning of Example 3 is the same as that of Example 2, except that during the preparation of the polypyrrole nanosilver loaded nanocellulose conductive seasoning, 1.53 kg of sodium bromide is first added and mixed evenly, and then 5.19 kg of sodium dodecylbenzenesulfonate is added and mixed evenly. The remaining steps are the same as those of Example 2.

[0032] The following is the application of polypyrrole nanosilver loaded nanocellulose conductive seasoning in conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fiber Application Example 1 The conductive polylactic acid-polypyrrole nanosilver-loaded nanocellulose composite fiber of Application Example 1 is prepared by the following steps: S1, melt-mixing 13 kg of polypyrrole nanosilver loaded nanocellulose conductive seasoning and 87 kg of polylactic acid to prepare a conductive masterbatch; S2. Weigh 90 kg of conductive masterbatch and 180 kg of polylactic acid spinning melt. Using a twin-screw extruder system, separately control the melting and delivery of the (conductive masterbatch) core layer and the (polylactic acid spinning melt) skin layer. Extrude the core layer from the inner hole and the skin layer from the outer ring to produce a conductive polylactic acid-polypyrrole nanosilver-loaded nanocellulose composite fiber with a sheath-core structure, wherein the sheath component is the conductive masterbatch and the polylactic acid spinning melt is the core component. The polypyrrole nanosilver-loaded nanocellulose conductive seasoning is the polypyrrole nanosilver-loaded nanocellulose conductive seasoning prepared in Example 1.

[0033] Application Example 2 The conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fiber of Application Example 2 is prepared by the following operating steps: S1, melt mixing 13 kg of polypyrrole nanosilver loaded nanocellulose conductive seasoning with 87 kg of polylactic acid to obtain a conductive masterbatch; S2, weighing 90 kg of conductive masterbatch and 210 kg of polylactic acid spinning melt, using a twin-screw extrusion system to control the melting and transportation of the conductive masterbatch and the polylactic acid spinning melt respectively, extruding the conductive masterbatch through the inner hole and extruding the polylactic acid spinning melt through the outer ring, to obtain a conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fiber with a skin-core structure in which the skin component is the conductive masterbatch and the polylactic acid spinning melt is the core component.

[0034] The polypyrrole nano-silver loaded nano-cellulose conductive seasoning is the polypyrrole nano-silver loaded nano-cellulose conductive seasoning prepared in Example 1.

[0035] Application Example 3 The conductive polylactic acid-polypyrrole nanosilver-loaded nanocellulose composite fiber of Application Example 3 is prepared by the following steps: S1, melt-mixing 13 kg of polypyrrole nanosilver loaded nanocellulose conductive seasoning and 87 kg of polylactic acid to prepare a conductive masterbatch; S2. Add 90 kg of conductive masterbatch into 225 kg of polylactic acid spinning melt to prepare conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers with a sheath-core structure in which the sheath component is the conductive masterbatch and the polylactic acid spinning melt is the core component.

[0036] The polypyrrole nano-silver loaded nano-cellulose conductive seasoning is the polypyrrole nano-silver loaded nano-cellulose conductive seasoning prepared in Example 1.

[0037] Application Examples 4-5 The difference between the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fiber of Application Example 4-5 and Application Example 2 is that the polypyrrole nanosilver loaded nanocellulose conductive seasoning is the polypyrrole nanosilver loaded nanocellulose conductive seasoning prepared in Example 2-3, and the remaining steps are the same as Application Example 2.

[0038] Application Example 6 The preparation method of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fiber in Application Example 6 differs from that in Application Example 5 in that 17.4 kg of nanohydroxyapatite is added when the polypyrrole nanosilver loaded nanocellulose conductive seasoning and polylactic acid are melt-mixed in step S1, and the remaining steps are the same as those in Application Example 5.

[0039] Application Example 7 The preparation method of the conductive polylactic acid-polypyrrole nanosilver-loaded nanocellulose composite fiber in Application Example 7 is different from that in Application Example 6 in that nanohydroxyapatite is replaced by carbon nanotubes, and the remaining steps are the same as those in Application Example 6.

[0040] Application Example 8 The preparation method of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fiber in Application Example 8 differs from that in Application Example 6 in that in step S1, 16.6 kg of nanohydroxyapatite and 800 g of acetyl tributyl citrate are added when the polypyrrole nanosilver loaded nanocellulose conductive seasoning and polylactic acid are melt-mixed, and the remaining steps are the same as those in Application Example 6.

[0041] Application Example 9 The preparation method of the conductive polylactic acid-polypyrrole nanosilver-loaded nanocellulose composite fiber in Application Example 9 is different from that in Application Example 8 in that nanohydroxyapatite is replaced by carbon nanotubes, and the remaining steps are the same as those in Application Example 8.

[0042] Application Examples 10-13 The preparation method of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fiber of Application Examples 10-13 is the same as that of Application Example 9, except that the amounts of carbon nanotubes and acetyl tributyl citrate used are 16.7 kg and 700 g, 16.9 kg and 500 g, 17.0 kg and 400 g, and 17.05 kg and 350 g, respectively, and the remaining steps are the same as those of Application Example 9.

[0043] Comparative Application Example 1 The difference between the preparation method of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fiber in Application Example 1 and that in Application Example 1 is that step S3 is not performed when preparing the polypyrrole nanosilver loaded nanocellulose conductive seasoning to obtain the nanosilver loaded nanocellulose conductive seasoning, and the remaining steps are the same as those in Application Example 1.

[0044] Application Comparative Example 2 The difference between the preparation method of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fiber of Application Example 2 and that of Application Example 1 is that the polypyrrole nanosilver loaded nanocellulose conductive seasoning is prepared by the following steps: adding 1 kg of pyrrole monomer to 1 kg of nanocellulose suspension, then adding 0.817 kg of sodium bromide, and finally adding ferric chloride hexahydrate under stirring conditions to prepare the polypyrrole loaded nanocellulose conductive seasoning.

[0045] Application Comparative Example 3 The difference between the preparation method of the conductive polylactic acid polypyrrole nanosilver-loaded nanocellulose composite fiber of Application Example 3 and that of Application Example 1 is that: in the process of preparing the polypyrrole nanosilver-loaded nanocellulose conductive seasoning, after adding pyrrole monomer to the nanosilver-loaded nanocellulose suspension, sodium bromide (dopant) is not added, and the remaining steps are the same as those of Application Example 1.

[0046] Comparative Application Example 4 The difference between the preparation method of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fiber of Application Example 4 and that of Application Example 1 is that in the process of preparing the polypyrrole nanosilver loaded nanocellulose conductive seasoning, step S1 directly adds silver nitrate solution to the nanocellulose suspension without mixing it with phytic acid solution, and the remaining steps are the same as those of Application Example 1.

[0047] Performance testing The following testing standards or methods were used to test the performance of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers obtained in different application examples 1-13 and application comparison examples 1-4. The test results are shown in Table 1.

[0048] Tensile strength: The tensile strength of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers was tested in accordance with GB / T 14342-2015 “Test method for specific electrical resistivity of chemical fiber staple fibers”.

[0049] Bending strength: The flexural strength of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers was tested according to ASTM D638-14 "Plastic Tensile Test Standard".

[0050] Volume conductivity: The volume conductivity of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fiber was tested in accordance with GB / T 1410-2006 “Test method for volume resistivity and surface resistivity of solid insulating materials”.

[0051] Table 3 Performance test results of different conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers The test results in Table 1 show that the tensile strength and flexural strength of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers obtained in this application are as high as 215 MPa and 305 MPa, respectively, and have high mechanical properties. In addition, the volume conductivity of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers is as high as 1.35×10 -4 S / cm, which improves the conductivity of nanocellulose.

[0052] Combined with the performance test data of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers of application examples 1-3, it was found that the volume conductivity of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers of application example 2 was 1.19×10 -4 S / cm, which are higher than those in Application Example 1 and Application Example 3, indicating that when the mass ratio of the sheath component to the core component in the step S2 of preparing the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fiber is 1: (2-2.5), the conductivity of nanocellulose can be improved.

[0053] Combining the performance test data of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers of application examples 4 and 2, it was found that the volume conductivity of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers of application example 4 was 1.21×10 -4 S / cm, which are higher than those in Application Example 2, indicating that when sodium bromide and sodium dodecylbenzenesulfonate are selected as dopants in step S2, and sodium bromide and sodium dodecylbenzenesulfonate in the same amount as pyrrole monomers and other substances are added at the same time, the conductivity of nanocellulose can be improved.

[0054] Combining the performance test data of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers of Application Example 4 and Application Example 5, it was found that the volume conductivity of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers of Application Example 5 was 1.22×10 -4 S / cm, which is higher than that in Application Example 4. Compared with adding sodium bromide and sodium dodecylbenzenesulfonate at the same time, adding sodium bromide and sodium dodecylbenzenesulfonate in sequence can further improve the conductivity of nanocellulose.

[0055] Combining the performance test data of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers of Application Example 5 and Application Example 6, it was found that the volume conductivity of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers of Application Example 6 was 1.23×10 -4 S / cm, which are all higher than those in Application Example 5, indicating that when inorganic particles are added when the polypyrrole nanosilver-loaded nanocellulose conductive seasoning and polylactic acid are melt-mixed in step S1 of preparing the conductive polylactic acid polypyrrole nanosilver-loaded nanocellulose composite fiber, and the inorganic particles are nanohydroxyapatite, the conductivity of the nanocellulose can be improved.

[0056] Combining the performance test data of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers of Application Example 6 and Application Example 7, it was found that the volume conductivity of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers of Application Example 7 was 1.24×10 -4 S / cm, which is higher than that of Application Example 6, indicating that the conductivity of nanocellulose can be further improved by replacing nanohydroxyapatite with carbon nanotubes.

[0057] Combining the performance test data of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers of Application Example 8 and Application Example 7, it was found that the volume conductivity of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers of Application Example 8 was 1.25×10 -4 S / cm, which is higher than that of Application Example 6, indicating that the addition of nanohydroxyapatite and acetyl tributyl citrate when the polypyrrole nanosilver-loaded nanocellulose conductive seasoning and polylactic acid are melt-mixed in step S1 can further improve the conductivity of nanocellulose.

[0058] Combining the performance test data of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers of Application Example 8 and Application Example 9, it was found that the volume conductivity of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers of Application Example 9 was 1.26×10 -4 S / cm, which is higher than that of Application Example 6, indicating that replacing nanohydroxyapatite with carbon nanotubes and adding acetyl tributyl citrate simultaneously can further improve the conductivity of nanocellulose.

[0059] Combined with the performance test data of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers of application examples 9-13, it was found that the volume conductivity of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers of application examples 10-12 was 1.27×10 -4 ~1.29×10 -4 S / cm, which are higher than those in Application Example 9 and Application Example 13, indicating that when carbon nanotubes are added in step S1 of preparing conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers, acetyl tributyl citrate is also added; when the mass ratio of acetyl tributyl citrate to carbon nanotubes is 1: (25-45), the conductivity of nanocellulose can be improved.

[0060] In addition, combining the various index data of the conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers of application examples 1-4 and application example 1, it was found that the conductivity of nanocellulose can be improved by using the polypyrrole nanosilver loaded nanocellulose conductive seasoning obtained in this application to prepare conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fibers.

[0061] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A method for preparing a polypyrrole nanosilver loaded nanocellulose conductive seasoning, characterized in that: The following steps are included: S1. Prepare a nanocellulose suspension with a mass fraction of 1-3%, a phytic acid solution with a mass fraction of 1%, a silver nitrate solution with a mass fraction of 6-8%, and a glucose solution with a mass fraction of 3-10% respectively; S2. First, the nanocellulose suspension is mixed with the phytic acid solution, stirred at 200-300 r / min for 0.5-2 h, then the silver nitrate solution is added, stirred at 500-1000 r / min for 0.5-1 h, and then the glucose solution is added, and ultrasonic treatment is performed to obtain a nanosilver-loaded nanocellulose suspension; S3. Adding pyrrole monomer of the same mass as the nanosilver-loaded nanocellulose suspension to the nanosilver-loaded nanocellulose suspension, then adding a dopant, and finally adding ferric chloride hexahydrate under stirring conditions to prepare a polypyrrole nanosilver-loaded nanocellulose conductive seasoning.

2. The method for preparing the polypyrrole nanosilver loaded nanocellulose conductive seasoning according to claim 1, wherein: In the step S2, the dopants are sodium bromide and sodium dodecylbenzene sulfonate, and the sodium bromide and the sodium dodecylbenzene sulfonate are added in the same amount as the pyrrole monomer and the like.

3. The method for preparing the polypyrrole nanosilver loaded nanocellulose conductive seasoning according to claim 1, wherein: The nanocellulose in the nanocellulose suspension is one or more of cellulose nanocrystals, cellulose nanowires, cellulose microwires and bacterial cellulose.

4. A conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fiber, characterized in that: The invention comprises the following raw materials: polylactic acid and a polypyrrole nano-silver loaded nano-cellulose conductive seasoning prepared by the preparation method according to any one of claims 1 to 3.

5. A method for preparing the conductive polylactic acid-polypyrrole nanosilver-loaded nanocellulose composite fiber according to claim 4, characterized in that: The following steps are included: S1, melt-mixing polypyrrole nanosilver loaded nanocellulose conductive seasoning and polylactic acid to prepare a conductive masterbatch with a mass fraction of polypyrrole nanosilver loaded nanocellulose conductive seasoning of 10-15%; S2. Weigh the conductive masterbatch and polylactic acid spinning melt, use a twin-screw extrusion system to control the melting and transportation of the conductive masterbatch and the polylactic acid spinning melt respectively, extrude the conductive masterbatch from the inner hole and extrude the polylactic acid spinning melt from the outer ring, and obtain a conductive polylactic acid polypyrrole nanosilver loaded nanocellulose composite fiber with a skin-core structure in which the skin component is the conductive masterbatch and the polylactic acid spinning melt is the core component.

6. The method for preparing the conductive polylactic acid-polypyrrole nanosilver-loaded nanocellulose composite fiber according to claim 5, characterized in that: The mass ratio of the sheath component to the core component in step S2 is 1:(2-2.5).

7. The method for preparing the conductive polylactic acid-polypyrrole nanosilver-loaded nanocellulose composite fiber according to claim 5, characterized in that: In the step S1, inorganic particles are added when the polypyrrole nanosilver loaded nanocellulose conductive seasoning and polylactic acid are melt-mixed; the mass ratio of the inorganic particles to the polylactic acid is 1:(3-7).

8. The method for preparing the conductive polylactic acid-polypyrrole nanosilver-loaded nanocellulose composite fiber according to claim 7, characterized in that: The inorganic particles are carbon nanotubes.

9. The method for preparing the conductive polylactic acid-polypyrrole nanosilver-loaded nanocellulose composite fiber according to claim 8, characterized in that: Acetyl tributyl citrate is also added when adding carbon nanotubes in step S1; the mass ratio of acetyl tributyl citrate to carbon nanotubes is 1:(25-45).

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