阅读说明：本技术 一种石墨烯与纳米纤维素改性的复合纤维及其制备方法 (Graphene and nanocellulose modified composite fiber and preparation method thereof ) 是由 吴敏 黄勇 赵阳 于 2019-11-19 设计创作，主要内容包括：本发明属于纺织品领域,具体涉及一种石墨烯与纳米纤维素改性的复合纤维及其制备方法。本发明提供的石墨烯纳米改性复合纤维其中,包括99.0％～99.9％的树脂,石墨烯和纳米纤维素作为纳米改性填料,二者的总质量添加含量为0.1％～1.0％,所述的石墨烯和纳米纤维素的质量比为1：9～9：1。石墨烯和纳米纤维素由于静电相互作用可以改善单一填料在树脂基体的分散性。将该复合材料经纺丝设备制备功能纤维并纺成纤维,该纤维具有强度高、耐磨、透气、抗静电、远红外发热以及抗菌等性能。本发明的工艺简单、产品性能优异,适用于功能性服饰的特殊需求。(The invention belongs to the field of textiles, and particularly relates to a graphene and nanocellulose modified composite fiber and a preparation method thereof. The graphene nano-modified composite fiber provided by the invention comprises 99.0-99.9% of resin, graphene and nano-cellulose are used as nano-modified fillers, the total mass addition content of the graphene and the nano-cellulose is 0.1-1.0%, and the mass ratio of the graphene to the nano-cellulose is 1: 9-9: 1. graphene and nanocellulose can improve the dispersibility of a single filler in a resin matrix due to electrostatic interaction. The composite material is spun into fiber through functional fiber prepared with spinning equipment, and the fiber has the advantages of high strength, wear resistance, air permeability, static resistance, far infrared heating, bacteria resistance and the like. The invention has simple process and excellent product performance, and is suitable for special requirements of functional clothes.)

1. The graphene and nanocellulose modified composite fiber is characterized by comprising the following components in percentage by weight: 99.0% -99.9% of resin and 0.1% -1.0% of graphene and nano-cellulose in total, wherein the weight ratio of the added graphene to the added nano-cellulose is 1: 9-9: 1.

2. the graphene and nanocellulose modified composite fibre according to claim 1, wherein said graphene and nanocellulose modified composite fibre comprises, in weight percent: 99.4-99.8% of resin and 0.2-0.6% of graphene and nano-cellulose in total, wherein the weight ratio of the added graphene to the added nano-cellulose is 3: 1-1: 3.

3. The graphene and nanocellulose modified composite fiber according to claim 1 or 2, wherein the resin comprises one or more of nylon 6, polyethylene terephthalate, polybutylene terephthalate and polyacrylonitrile.

4. The graphene and nanocellulose modified composite fibre according to claim 1 or 2, wherein said graphene comprises single-layer graphene and/or few-layer graphene.

5. The graphene and nanocellulose modified composite fibre according to claim 1 or 2, wherein said nanocellulose comprises unmodified nanocellulose and/or modified nanocellulose; wherein the unmodified nano-cellulose comprises one or more of unmodified nano-cellulose whiskers, unmodified nano-cellulose fibers, unmodified wood nano-cellulose, unmodified cellulose microfibrils, unmodified wood cellulose microfibrils and unmodified bacterial cellulose; the modified nano-cellulose is obtained by modifying functional groups of unmodified micro-nano-cellulose on the basis of the unmodified micro-nano-cellulose, wherein the functional groups of the modified micro-nano-cellulose comprise one or more of alkyl, cycloalkyl, heterocyclic groups, aromatic groups, alkoxy groups, ester groups, acyl, amino and isocyanate groups.

6. A method for preparing the graphene and nanocellulose modified composite fiber according to any one of claims 1 to 5, comprising the steps of:

1) carrying out melt blending extrusion granulation on graphene, nano cellulose and resin on a double-screw extruder to obtain a composite material master batch;

2) and carrying out melt spinning on the dried composite material master batch on spinning equipment to obtain the graphene nano cellulose modified composite fiber.

7. The preparation method according to claim 6, wherein the melt blending extrusion granulation temperature in the step 1) is 20-40 ℃ higher than the melting temperature of the resin.

Technical Field

The invention belongs to the field of textiles, and particularly relates to a graphene and nanocellulose modified composite fiber and a preparation method thereof.

Background

Over 100 years ago, the raw materials of the textile are mainly derived from natural substances, such as cotton, hemp, silk, wool and the like, and the natural fibers are obtained with higher cost and longer growth cycle. Later, with the development of the polymer synthesis industry, synthetic fibers, which are chemical fibers prepared by spinning, molding and post-treating synthetic linear polymers having suitable molecular weights, have gradually appeared and become widely used. Compared with natural fibers, the synthetic fibers have the advantages of high strength, good elasticity, mildew and moth resistance and the like, but have the defects of poor air permeability, poor heat retention and the like.

Graphene is a two-dimensional carbon material with the highest strength and the best electrical property, and the mechanical strength, the wear resistance and the antistatic effect of the fiber can be obviously improved by adding the graphene into a resin matrix. In addition, research results show that the graphene has good antibacterial performance and a far infrared absorption function, so that the synthetic fiber is expected to have better antibacterial performance and self-warming property when the graphene is added into resin to prepare the fiber. However, graphene has a large specific surface area (generally 2630 m)²About/g), and the two-dimensional sheet layers are easy to agglomerate in the resin due to the existence of Van der Waals force, so that the dispersion effect is damaged, and the fiber performance of the composite material is seriously reduced.

To address this problem, researchers have adopted many different approaches to improve. The patent application with the application number of 201710952633.6 disperses graphene into caprolactam water solution, then carries out polymerization reaction to obtain graphene/nylon 6 with high dispersibility, and then obtains graphene nylon 6 composite fibers through melt spinning. In the patent application with the patent application number of 201711007680.X, a surfactant and a coupling agent are used for carrying out surface dispersion treatment on graphene, and the treated graphene, nylon and a heat stabilizer are granulated in a double-screw extruder to obtain the composite material. The patent application with the patent application number of 201810903390.1 blends graphene fiber with the graphene content of 0.4-0.8% with cotton fiber to obtain the composite fiber blended by the two fibers.

The methods improve the dispersibility of graphene to a certain extent, but simultaneously change the process route of the fiber synthesis industry (adding graphene in the polymerization process), or introduce more chemical substances (heat stabilizer, coupling agent and the like) or increase the spinning process (blending), and have different defects.

Disclosure of Invention

The invention aims to develop a formula and a preparation method of a graphene and nanocellulose modified composite fiber, which can obviously improve the dispersibility of graphene and nanocellulose in a resin matrix. In addition, the addition of the functional nano-filler graphene and the nano-cellulose can obviously improve the strength, the wear resistance, the antistatic property, the antibacterial property and the heat retention property of the composite fiber. In addition, the whole spinning process does not need to add extra process and equipment, and the energy is saved and the environment is protected.

The specific technical scheme of the invention is as follows:

the graphene and nano-cellulose modified composite fiber comprises the following components in percentage by weight: 99.0% -99.9% of resin and 0.1% -1.0% of graphene and nano-cellulose in total, wherein the weight ratio of the added graphene to the added nano-cellulose is 1: 9-9: 1.

further preferably, the graphene and nanocellulose modified composite fiber comprises the following components in percentage by weight: 99.4-99.8% of resin and 0.2-0.6% of graphene and nano-cellulose in total, wherein the weight ratio of the added graphene to the added nano-cellulose is 3: 1-1: 3.

The graphene and nano-cellulose modified composite fiber is characterized in that one or more of nylon 6(PA6), polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and Polyacrylonitrile (PAN) are adopted.

The graphene and nanocellulose modified composite fiber according to the invention, wherein the graphene includes but is not limited to single-layer graphene and/or few-layer graphene.

The graphene and nanocellulose modified composite fiber is characterized in that the nanocellulose comprises unmodified nanocellulose and/or modified nanocellulose; wherein the unmodified nano-cellulose comprises one or more of unmodified nano-cellulose whiskers, unmodified nano-cellulose fibers, unmodified wood nano-cellulose, unmodified cellulose microfibrils, unmodified wood cellulose microfibrils and unmodified bacterial cellulose; the modified nano-cellulose is obtained by modifying functional groups of unmodified micro-nano-cellulose on the basis of the unmodified micro-nano-cellulose, wherein the functional groups of the modified micro-nano-cellulose comprise one or more of alkyl, cycloalkyl, heterocyclic groups, aromatic groups, alkoxy groups, ester groups, acyl, amino and isocyanate groups.

The invention also provides a preparation method of any one of the graphene and nanocellulose modified composite fibers, which specifically comprises the following steps:

1) carrying out melt blending extrusion granulation on graphene, nano cellulose and resin on a double-screw extruder to obtain a composite material master batch;

2) and carrying out melt spinning on the dried composite material master batch on spinning equipment to obtain the graphene nano cellulose modified composite fiber.

The melt blending extrusion granulation and melt spinning involved in the present invention can be performed using techniques well known in the art. As a preference and not a limitation, the melt blending extrusion granulation and melt spinning may be specifically: mixing and stirring the graphene, the nano cellulose powder and the resin in a high-speed blender for 10-20 minutes to uniformly mix the materials, taking out the mixed material, and carrying out extrusion granulation in a double-screw extruder, wherein the processing temperature of the extruder is preferably higher than the melting temperature of the resin by 20-40 ℃. And adding the resin master batch obtained by extrusion granulation into a melt spinning machine, melting the mixture, conveying the mixture into a spinning part, conveying the mixture into a spinning assembly through a metering pump, and filtering the mixture and then extruding the mixture through capillary holes of a spinneret plate. The liquid silk is gradually solidified through a cooling medium, and is drawn into as-spun fiber silk at high speed through a winding device, and the as-spun fiber is post-processed into the required fiber.

Cellulose molecules are linear polymers formed by repeatedly connecting beta-D-glucose through beta (1-4) glycosidic bonds, in a cellulose crystal structure, a large number of hydroxyl groups exist in a glucose ring plane between two parallel molecular chains, so that the cellulose molecular chains are hydrophilic due to more-OH, -O and other groups in a direction parallel to the glucose ring, and are hydrophobic due to more C-H groups in a direction vertical to the glucose ring. When cellulose and graphene are dispersed in a resin matrix, the hydrophobic surface of the cellulose chain follows the graphene SP²Aromatic ring arrangement of hybrid orbitals, CH-and graphene SP on the hydrophobic surface of cellulose molecular chains²The hybridized pi bonds are interacted, namely CH-pi interaction, graphene and nano cellulose are added into the resin matrix together, and the stability of the graphene and the nano cellulose in the resin matrix can be improved through the coordination interaction of the two fillers. According to the invention, the dispersion of graphene in the resin matrix is effectively improved by adding the environment-friendly nano-cellulose, and in addition, the air permeability of the synthetic fiber is improved by adding the biomass-based nano-cellulose.

Graphene and nanocellulose can improve the dispersibility of a single filler in a resin matrix due to electrostatic interaction. The composite material is spun into fiber through functional fiber prepared with spinning equipment, and the fiber has the advantages of high strength, wear resistance, air permeability, static resistance, far infrared heating, bacteria resistance and the like. The invention has simple process and excellent product performance, and is suitable for special requirements of functional clothes.

Specifically, the present invention has the following advantages:

1. according to the technical scheme provided by the invention, the nano-cellulose and the graphene are utilized to endow the fibers with functionality, and the graphene and the nano-cellulose can synergistically improve the dispersibility of the graphene and the nano-cellulose in a resin matrix due to an electrostatic effect.

2. The nano-cellulose and the graphene can obviously improve the strength, the wear resistance, the antistatic property, the antibacterial property and the heat preservation property of the resin matrix.

3. The raw materials for preparing the nano-cellulose and the graphene are natural fibers and graphite, and have rich sources and low price.

4. The technical scheme provided by the invention is simple in process and environment-friendly.

Drawings

Fig. 1 is a schematic diagram of a graphene and nanocellulose modified composite fiber according to the present invention.

Detailed Description

The present invention will be further described with reference to the following specific examples.

Example 1

Mixing 2 parts of nano cellulose whisker, 3 parts of single-layer graphene and 999 parts of polybutylene terephthalate (PBT) resin in a mixer for 15 minutes, taking out the mixed material, and carrying out extrusion granulation in a double-screw extruder, wherein the processing temperature of the extruder is higher than the melting temperature of the resin by 30 ℃. And adding the resin master batch obtained by extrusion granulation into a melt spinning machine, melting the mixture, conveying the mixture into a spinning part, conveying the mixture into a spinning assembly through a metering pump, and filtering the mixture and then extruding the mixture through capillary holes of a spinneret plate. The liquid silk is gradually solidified through a cooling medium, and is stretched into nascent fiber silk at a high speed through a winding device, and the nascent fiber is post-processed to prepare the graphene and nano-cellulose modified composite fiber. The prepared graphene and nanocellulose modified composite fiber is shown in fig. 1. Compared with the original PBT fiber, the tensile strength of the fiber is improved by 15 percent, and the modulus is improved by 10 percent.

Example 2

Mixing 0.5 part of nano cellulose whisker, 0.5 part of few-layer graphene and 999 parts of nylon 6 resin in a mixer for 10 minutes, taking out the mixed material, and carrying out extrusion granulation in a double-screw extruder, wherein the processing temperature of the extruder is 20 ℃ higher than the melting temperature of the resin. And adding the resin master batch obtained by extrusion granulation into a melt spinning machine, melting the mixture, conveying the mixture into a spinning part, conveying the mixture into a spinning assembly through a metering pump, and filtering the mixture and then extruding the mixture through capillary holes of a spinneret plate. The liquid silk is gradually solidified through a cooling medium, and is stretched into nascent fiber silk at a high speed through a winding device, and the nascent fiber is post-processed to prepare the graphene and nano-cellulose modified composite fiber.

Example 3

After 0.5 part of nano cellulose fiber, 4.5 parts of few-layer graphene and 995 parts of nylon 6 resin are mixed in a mixer for 20 minutes, the mixture is taken out and extruded and granulated in a double-screw extruder, and the processing temperature of the extruder is higher than the melting temperature of the resin by 40 ℃. And adding the resin master batch obtained by extrusion granulation into a melt spinning machine, melting the mixture, conveying the mixture into a spinning part, conveying the mixture into a spinning assembly through a metering pump, and filtering the mixture and then extruding the mixture through capillary holes of a spinneret plate. The liquid silk is gradually solidified through a cooling medium, and is stretched into nascent fiber silk at a high speed through a winding device, and the nascent fiber is post-processed into graphene and nano-cellulose modified composite fiber, so that the graphene and nano-cellulose modified composite fiber is prepared.

Example 4

Mixing 2 parts of acyl chloride modified nano cellulose fiber, 8 parts of few-layer graphene and 990 parts of polyacrylonitrile resin in a mixer for 15 minutes, taking out the mixed material, and performing extrusion granulation in a double-screw extruder, wherein the processing temperature of the extruder is 25 ℃ higher than the melting temperature of the resin. And adding the resin master batch obtained by extrusion granulation into a melt spinning machine, melting the mixture, conveying the mixture into a spinning part, conveying the mixture into a spinning assembly through a metering pump, and filtering the mixture and then extruding the mixture through capillary holes of a spinneret plate. The liquid silk is gradually solidified through a cooling medium, and is stretched into nascent fiber silk at a high speed through a winding device, and the nascent fiber is post-processed into graphene and nano-cellulose modified composite fiber, so that the graphene and nano-cellulose modified composite fiber is prepared.

Example 5

Mixing 1 part of anhydride modified nano cellulose fiber, 4 parts of few-layer graphene and 995 parts of nylon 6 resin in a mixer for 12 minutes, taking out the mixed material, and performing extrusion granulation in a double-screw extruder, wherein the processing temperature of the extruder is higher than the melting temperature of the resin by 35 ℃. And adding the resin master batch obtained by extrusion granulation into a melt spinning machine, melting the mixture, conveying the mixture into a spinning part, conveying the mixture into a spinning assembly through a metering pump, and filtering the mixture and then extruding the mixture through capillary holes of a spinneret plate. The liquid silk is gradually solidified through a cooling medium, and is stretched into nascent fiber silk at a high speed through a winding device, and the nascent fiber is post-processed into graphene and nano-cellulose modified composite fiber, so that the graphene and nano-cellulose modified composite fiber is prepared.

Example 6

After 4 parts of bacterial cellulose fiber, 1 part of single-layer graphene and 995 parts of polyethylene terephthalate (PET) are mixed in a mixer for 15 minutes, the mixture is taken out and extruded and granulated in a double-screw extruder, and the processing temperature of the extruder is 30 ℃ higher than the melting temperature of the resin. And adding the resin master batch obtained by extrusion granulation into a melt spinning machine, melting the mixture, conveying the mixture into a spinning part, conveying the mixture into a spinning assembly through a metering pump, and filtering the mixture and then extruding the mixture through capillary holes of a spinneret plate. The liquid silk is gradually solidified through a cooling medium, and is stretched into nascent fiber silk at a high speed through a winding device, and the nascent fiber is post-processed into graphene and nano-cellulose modified composite fiber, so that the graphene and nano-cellulose modified composite fiber is prepared.

Example 7

After 4.5 parts of bacterial cellulose fiber, 0.5 part of single-layer graphene and 995 parts of polyethylene terephthalate (PET) are mixed in a mixer for 10 minutes, the mixture is taken out and extruded and granulated in a double-screw extruder, and the processing temperature of the extruder is 20 ℃ higher than the melting temperature of the resin. And adding the resin master batch obtained by extrusion granulation into a melt spinning machine, melting the mixture, conveying the mixture into a spinning part, conveying the mixture into a spinning assembly through a metering pump, and filtering the mixture and then extruding the mixture through capillary holes of a spinneret plate. The liquid silk is gradually solidified through a cooling medium, and is stretched into nascent fiber silk at a high speed through a winding device, and the nascent fiber is post-processed into graphene and nano-cellulose modified composite fiber, so that the graphene and nano-cellulose modified composite fiber is prepared.

Example 8

Mixing 2 parts of bacterial cellulose fiber, 2 parts of single-layer graphene and 996 parts of nylon 6 resin in a mixer for 20 minutes, taking out the mixed material, and performing extrusion granulation in a double-screw extruder, wherein the processing temperature of the extruder is 25 ℃ higher than the melting temperature of the resin. And adding the resin master batch obtained by extrusion granulation into a melt spinning machine, melting the mixture, conveying the mixture into a spinning part, conveying the mixture into a spinning assembly through a metering pump, and filtering the mixture and then extruding the mixture through capillary holes of a spinneret plate. The liquid silk is gradually solidified through a cooling medium, and is stretched into nascent fiber silk at a high speed through a winding device, the nascent fiber is post-processed into graphene and nano-cellulose modified composite fiber, and the graphene and nano-cellulose modified composite fiber is prepared.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.