CN108707319B - Graphene-terylene composite master batch and preparation method thereof - Google Patents
Graphene-terylene composite master batch and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
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- D06M11/54—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur dioxide; with sulfurous acid or its salts
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- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
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- D06M13/402—Amides imides, sulfamic acids
- D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
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- D06M2101/16—Synthetic fibres, other than mineral fibres
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- D06M2101/32—Polyesters
Abstract
The invention provides a graphene-terylene composite master batch and a preparation method thereof, wherein in the graphene-terylene composite master batch, the content of graphene relative to terylene polyester chips is 0.05-2%, and the content of biological protein powder relative to terylene polyester chips is 1.5-4.5%. The preparation method comprises the steps of graphene-terylene composite powder preparation, bioprotein-terylene composite powder preparation, mixing and extrusion; the graphene-terylene composite fiber prepared by spinning the graphene-terylene composite master batch prepared by the invention has softer hand feeling, better skin-friendly property, good moisture absorption performance and no generation of static electricity, and meanwhile, the friction force between the fibers is increased, the cohesive force is enhanced, and the spinnability of the terylene fiber is obviously improved.
Description
Technical Field
The invention provides a polyester master batch and a preparation method thereof, and particularly relates to a graphene-polyester composite master batch and a preparation method thereof.
Background
Graphene (Graphene) is a two-dimensional carbon nanomaterial composed of carbon atoms in sp hybridized orbitals into a hexagonal honeycomb lattice. The graphene has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like, and is considered to be a revolutionary material in the future.
In recent years, functional and differential fibers represented by graphene are rapidly developed, and the modified and modified graphene is added into the production process of the fibers, so that the prepared graphene fibers have good strength, antibacterial performance and far infrared release function, and therefore, the graphene fibers are more and more attracted by general attention of the industry and the society.
Generally speaking, the best choice of the graphene-terylene nano composite fiber is graphene oxide modified by halogenated hydrocarbon functionalization, and the modified graphene oxide has good compatibility with terylene polyester, which is beneficial to uniformly dispersing the graphene in a terylene polyester matrix, thereby improving the strength of the graphene-terylene nano composite fiber. Drying common industrial polyester chips, performing composite granulation with graphene with different components to prepare master batches, and preparing the graphene-polyester nano composite fiber on a melt spinning machine.
For example, the patent of the invention is a Chinese patent with the publication number of CN105200547A and the patent name of 'a preparation method of graphene-terylene nano composite fiber', and the main technical scheme is as follows: firstly, polyester chips and modified graphene are mixed to prepare graphene-polyester composite master batches, then the prepared master batches are prepared into graphene-polyester composite fibers through a spinning process, and the graphene-polyester composite fibers mainly solve the following problems: (1) the physical strength of the prepared graphene-nylon nano composite fiber is improved; (2) the prepared graphene-terylene composite fiber has the advantages of static resistance, antibiosis, radiation resistance, flame retardance, smoothness, coolness and the like.
In actual production, we find that graphene-polyester composite fibers prepared from graphene-polyester composite master batches produced by a conventional method are as disclosed in the above-mentioned patent, and the prepared graphene-polyester composite fibers have too smooth surfaces, so that the resultant fibers have extremely poor cohesive force, are fluffy, are not easy to form a net and polymerize, are difficult to form strips, even cause the strength reduction of yarns, have the risk of yarn breakage, have great adverse effect on spinning, and have poor spinnability. In general, the effect is not ideal when the yarn is treated by the surfactant to improve the cohesive force of the yarn fibers; waxing is used for assisting in improving cohesive force, although the effect is achieved, the defect still exists, the waxing process can be uniformly adhered to the surface of the yarn at normal temperature, the phenomenon that the yarn is too soft and is adhered to a cluster to block the needle eye of a weaving machine, the yarn is too hard and is not adhered to the cluster to fall off is avoided, and the difficulty is very high; the present invention has been made in view of the above problems.
Meanwhile, in the production of graphene-polyester composite fibers prepared from the graphene-polyester composite master batches, the inventor finds that other functional components are added, so that the functional components have influence on the strength of the prepared graphene-polyester composite fibers.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a graphene-terylene composite master batch, which is used for solving the problems of low strength, poor cohesive force and poor functionality of graphene-terylene composite fibers in the prior art and achieving the invention aims of improving the strength and cohesive force of the graphene-terylene composite fibers and improving the spinnability and functionality of the fibers, therefore, the invention adopts the specific technical scheme that:
the preparation method of the graphene-terylene composite master batch specifically comprises the following steps:
(1) preparation of graphene-terylene composite powder
And (3) crushing, grinding and mixing the polyester chips and the graphene through mechanical ball milling to prepare the graphene-polyester composite powder.
Preferably, the graphene is graphene oxide; the surface of the graphene oxide contains rich oxygen-containing groups such as hydroxyl, carboxyl and the like, so that the agglomeration phenomenon of the graphene can be reduced to the minimum extent in the mixing process, the graphene oxide is easier to disperse, and is more uniformly mixed with polyester chips.
Further, the graphene oxide is prepared from one or more of expandable graphite, natural flake graphite and spherical graphite; preferably graphene oxide prepared after oxidation of expandable graphite; the graphene oxide sheet layer prepared by oxidizing expandable graphite has complex appearance structure layers, more folds and larger specific surface, so that the graphene oxide sheet layer is more easily and firmly bonded with polyester chips.
Furthermore, the raw materials for preparing the graphene oxide include expandable graphite, natural flake graphite and spherical graphite, which have a mesh size of 80-150, for example, 80, 90, 95, 100, 120 and 150 meshes can be selected, but after extensive research and development and experiments by the inventors, the most preferable is 90-120 meshes. The graphene oxide prepared from graphite with different particle sizes has a large difference in surface structure, and the number of layers and surface functional groups has a large influence on the physical properties and functionality of the prepared graphene-terylene composite master batch.
Preferably, the intrinsic viscosity of the polyester chip is 0.55-0.60dl/g, the carboxyl end group content is 16-16.5mol/t, the diethylene glycol content is 8.3-85%, and the melting point is 245 ℃; the melting point, viscosity, carboxyl end group content of the polyester resin chip and the crystallinity of the polyester fiber, wherein the crystallinity is the manifestation of fibril crystallization in the fiber and directly influences the quality of the prepared graphene master batch and the strength of the fiber, and the selection of the polyester chip is also the result of long-term research and summary of the inventor.
(2) Preparation of biological protein-terylene composite powder
And (3) grinding and mixing the biological protein powder and the polyester chips through mechanical ball milling to prepare the biological protein-polyester composite powder.
Preferably, in the step (2), the biological protein powder is one or more of wool protein powder and silk fibroin powder; the preferable silk fibroin powder is silk fibroin powder, the wool protein powder is poorer in short-time solubility than the silk fibroin powder due to the influence of a surface cortex, and the skin-friendly performance of the graphene-terylene composite master batch prepared by adding the silk fibroin powder is better. Based on the method, the silk fibroin powder is selected, so that the production efficiency of subsequent production processing is improved, and meanwhile, the prepared polyester fiber has better skin-friendly property and softness.
Preferably, the adding amount of the biological protein powder is 1.5-4.5% of the mass of the polyester chips;
further, adding a functional additive into the biological protein-terylene composite powder; the functional additive comprises the following components: polyacrylamide, sorbitan monostearate, pentaerythritol; the addition amount of the functional additive is 10-30% of the biological protein powder; the functional additive comprises the following components in percentage by mass: 10-20%: 35-45%: 3 to 6 percent. The functional additive can greatly reduce the influence of swelling and denaturation of protein powder on the strength of the fiber in the post-treatment process.
(3) Mixing and extruding
Respectively drying the graphene-terylene composite powder prepared in the step (1), the bioprotein-terylene composite powder prepared in the step (2) and the polyester chips, then uniformly mixing in a high-speed kneading machine, finally adding the mixture into a feeding bin of a double-screw extruder, mixing and extruding at a certain temperature, and then feeding the strips into a granulator for granulation, thus obtaining the graphene-terylene composite master batch prepared by the invention.
Preferably, the drying temperature is 100-120 ℃, and the drying moisture content is below 40ppm, preferably less than 20 ppm. The moisture in the polyester chips seriously affects the performance of the prepared graphene-polyester composite master batch, the moisture content of the polyester chips which are not dried is usually about 0.4%, and the moisture in the polyester chips is removed to avoid severe hydrolysis in the subsequent spinning process.
According to the invention, the graphene-polyester composite master batch is prepared by preparing the graphene-polyester composite powder, preparing the bioprotein-polyester composite powder and mixing the bioprotein-polyester composite powder and the high-speed kneading machine respectively, so that the graphene and protein powder in the prepared graphene-polyester composite master batch are uniformly distributed, the agglomeration phenomenon is avoided, and the risk of broken ends is avoided in the subsequent spinning process of the graphene-polyester master batch.
According to the invention, the protein powder is added into the prepared graphene-terylene composite master batch, and the graphene-terylene fiber prepared by spinning the graphene-terylene composite master batch has softer hand feeling, better skin affinity, good moisture absorption performance and no generation of static electricity, and meanwhile, the friction force between the fibers is increased, the cohesive force is enhanced, and the fiber spinnability is obviously improved.
Furthermore, in the graphene-terylene composite master batch, the addition amount of the graphene relative to the terylene polyester chips is 0.05-2%, and the addition amount of the biological protein powder relative to the terylene polyester chips is 1.5-4.5%; wherein the addition amount of the graphene is preferably 0.05-0.5%; particularly, when the graphene oxide prepared by oxidizing the expandable graphite is adopted, the addition amount of the graphene oxide is preferably 0.05-0.1%, so that the production cost can be greatly reduced.
The amount of the bioprotein powder added is important for the present invention. In the research and development process, the inventor finds that when the addition amount of the biological protein powder is less than 1.5%, the strength of the fiber is strengthened, but the transverse friction force of the prepared graphene polyester fiber is not greatly changed due to the reduction of the addition amount of the biological protein powder, and the spinnability is not obviously improved. When the addition amount of the biological protein powder is more than 4.5%, the strength of the fiber is reduced by more than 20%, and obviously, the significance of actual production is basically not achieved.
Further, the length-diameter ratio of the double-screw extruder is 40: 1, the rotating speed of a host is 120-150Hz, and the granules are cut by water cooling; wherein the extrusion temperature of each zone of the double-screw extruder is respectively as follows: 268 ℃, 278 ℃, 282 ℃, 285 ℃ and 278 ℃. According to the invention, the graphene can be uniformly dispersed in the polyester at the temperature of each zone of the double-screw extruder, and the composite master batch can be stably prepared.
In addition, the invention also provides a preparation method of the graphene-terylene composite fiber, which mainly comprises the following steps:
feeding the graphene-terylene composite master batch prepared by the invention into a feeding bin, feeding the mixture into a spinning box through a screw extruder for spinning, then cooling, forming and oiling the mixture through a slow cooling device by cross air blow, stretching the mixture through a pair of rollers I, a pair of rollers II and a pair of rollers III, and finally winding the mixture to prepare the graphene-terylene composite fiber.
Wherein the temperature of the spinning box is 260-270 ℃; the temperature of the slow cooling device is 245-255 ℃; the temperature of the side blowing device is 35-40 ℃, the humidity is 55-60%, and the wind speed is 0.1-0.3 m/s; the rotating speed of the oil tanker for oiling is 25-30 r/min; the temperatures of the first roller pair, the second roller pair and the third roller pair are respectively 70-85 ℃, 95-100 ℃ and 125-135 ℃.
Further, after the cooling forming, a dissolving step is also included before oiling; the dissolving step aims to dissolve the protein powder attached to the surface layer of the fiber by treating the spun graphene-polyester composite fiber tows through a dissolving process, so that a certain concave-convex microstructure is formed on the surface of the graphene-polyester fiber, and the transverse friction force between the fibers is further improved, so that the purpose of improving the cohesive force of the fibers is achieved, and the purpose of improving the spinnability of the fibers is achieved.
The specific process of dissolution comprises:
placing the prepared graphene polyester fiber tows in a protease solution for enzyme treatment; in the protease solution, the enzyme treatment temperature is 45-65 ℃, and the enzyme treatment time is 10-30 min;
further, immersing the graphene polyester fiber tows subjected to enzyme treatment in a mixed solution of sodium bisulfite, guanidine hydrochloride and TCEP for treatment for 30-50 min; the temperature of the mixed solution is 50-85 ℃, the concentration of the sodium bisulfite in the mixed solution is 185g/L, and the concentration of the guanidine hydrochloride in the mixed solution is 200 g/L; the concentration of TCEP is 30-60 g/L.
Based on the dissolving process, the protein powder attached to the surface layer of the fiber is partially dissolved, so that a concave-convex microstructure is formed on the surface of the graphene polyester fiber, the transverse friction force between the fibers is improved, the cohesive force of the fibers is improved, and the spinnability of the fibers is finally improved.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
1. according to the invention, the graphene is added into the preparation of the polyester master batch, so that the prepared graphene-polyester composite master batch has good antibacterial property, antistatic property and heat-conducting property, and the electric conductivity is as high as 3.0 multiplied by 104S/cm, the sensitivity is more than 4.1, and the fabric is very suitable for wearing exercise detection, health detection and medical detection.
2. The graphene-terylene composite fiber prepared by spinning the graphene-terylene composite master batch prepared by the invention has softer hand feeling, better skin-friendly property and good moisture absorption performance, the moisture absorption performance is up to more than 9% in standard atmosphere with the relative humidity of 65%, static electricity is not generated, meanwhile, the friction force between the fibers is increased, the cohesive force is enhanced, and the spinnability of the terylene fiber is obviously improved.
3. According to the invention, the graphene-terylene composite master batch is uniformly distributed without agglomeration through the preparation of the graphene-terylene composite powder, the preparation of the bioprotein-terylene composite powder and the mixing of a high-speed kneading machine, the risk of breaking the ends is avoided in the subsequent spinning process of the graphene-terylene composite master batch, and the rate of breaking the ends is reduced by 41-45%.
4. The graphene oxide prepared by adopting expandable graphite is selected, and the aim of the invention can be achieved by adding a small amount of graphene oxide in the preparation process of the graphene polyester master batch; the addition of the graphene oxide is only 0.05-0.1%, so that the production cost can be greatly reduced.
5. When the graphene-polyester composite master batch prepared by the method is used for producing graphene-polyester composite fibers, a dissolving step is introduced in the post-spinning treatment process, and the spun graphene-polyester composite fiber tows are treated by a dissolving process to partially dissolve protein powder attached to the surface layer of the fibers, so that a certain concave-convex microstructure is formed on the surface of the graphene-polyester composite fibers, and the transverse friction force between the fibers is further improved, so that the purpose of improving the cohesive force of the fibers is achieved, and the spinnability of the fibers is further improved.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Embodiment 1 a preparation method of a graphene-terylene composite master batch specifically comprises the following steps:
(1) preparation of graphene-terylene composite powder
The preparation method comprises the steps of taking polyester chips and natural crystalline flake graphite with the mesh number of 90 as raw materials to prepare graphene oxide, and grinding and mixing the graphene oxide and the natural crystalline flake graphite through mechanical ball milling to prepare graphene-polyester composite powder. Wherein the polyester chip has the intrinsic viscosity of 0.55-0.60dl/g, the carboxyl end group content of 16-16.5mol/t, the diglycol content of 8.3-85 percent and the melting point of 245 ℃.
(2) Preparation of biological protein-terylene composite powder
Mixing the wool protein powder, the functional additive and the polyester chips through mechanical ball milling to prepare wool protein-polyester composite powder; wherein the addition amount of the wool protein powder is 1.5 percent of the mass of the polyester chips, and the functional additive comprises the following components: polyacrylamide, sorbitan monostearate, pentaerythritol; the addition amount of the functional additive is 15 percent of the biological protein powder; the functional additive comprises the following components in percentage by mass: 10: 32: 5.
(3) mixing and extruding
Drying the graphene-polyester composite powder prepared in the step (1), the wool protein-polyester composite powder prepared in the step (2) and polyester chips at the temperature of 100 ℃, wherein the dry moisture content is below 40ppm, uniformly mixing the powder and the polyester chips in a high-speed kneading machine, finally adding the mixture into a feeding bin of a double-screw extruder, mixing and extruding the mixture at a certain temperature, and feeding strips into a granulator for granulation to obtain the graphene-polyester composite master batch prepared in the invention.
In the prepared graphene-polyester composite master batch, the addition amount of graphene relative to polyester chips is 1%, and the addition amount of wool protein powder relative to polyester chips is 1.5%;
the length-diameter ratio of the double-screw extruder is 40: 1, water-cooling and granulating at the main machine rotating speed of 120 Hz; wherein the extrusion temperature of each zone of the double-screw extruder is respectively as follows: 268 ℃, 278 ℃, 282 ℃, 285 ℃ and 278 ℃.
Feeding the prepared graphene-terylene composite master batch into a feeding bin, feeding the mixture into a spinning box through a screw extruder for spinning, then cooling, forming and oiling the mixture through a slow cooling device and cross air blowing, stretching the mixture through a pair of rollers I, a pair of rollers II and a pair of rollers III, and finally winding the mixture to prepare the graphene-terylene composite fiber.
Wherein, in the spinning process, the temperature of the spinning box is 270 ℃; the temperature of the slow cooling device is 255 ℃; the temperature of the side blowing device is 40 ℃, the humidity is 55 percent, and the wind speed is 0.1 m/s; the rotation speed of the oil tanker is 25 r/min; the temperatures of the first roller pair, the second roller pair and the third roller pair are respectively 70 ℃, 95 ℃ and 125 ℃.
After cooling and forming, the method also comprises a dissolving step before oiling; the specific process of dissolution comprises:
firstly, placing the prepared graphene polyester fiber tows in a protease solution for enzyme treatment; in the protease solution, the enzyme treatment temperature is 45 ℃, and the enzyme treatment time is 30 min; then immersing the graphene polyester fiber tows subjected to enzyme treatment into a mixed solution of sodium bisulfite, guanidine hydrochloride and TCEP for treatment for 30 min; the temperature of the mixed solution is 50 ℃, the concentration of sodium bisulfite in the mixed solution is 150g/L, and the concentration of guanidine hydrochloride in the mixed solution is 160 g/L; the concentration of TCEP was 30 g/L.
Based on the graphene-terylene composite fiber prepared from the graphene-terylene composite master batch, the graphene-terylene composite fiber has good spinnability, soft hand feeling, and excellent antistatic property and antibacterial property.
Embodiment 2 a preparation method of a graphene-terylene composite master batch specifically comprises the following steps:
(1) preparation of graphene-terylene composite powder
The preparation method comprises the steps of crushing, grinding and mixing the polyester chips and graphene oxide prepared from expandable graphite with the mesh number of 100 serving as raw materials through mechanical ball milling to prepare graphene-polyester composite powder. Wherein the polyester chip has the intrinsic viscosity of 0.55-0.60dl/g, the terminal carboxyl content of 16-16.5mol/t, the diglycol content of 8.3-85 percent and the melting point of 245 ℃.
(2) Preparation of biological protein-terylene composite powder
And (3) grinding and mixing the silk fibroin powder and polyester chips through mechanical ball milling to prepare the silk fibroin-polyester composite powder.
The adding amount of the biological protein powder is 3 percent of the mass of the polyester chips;
adding a functional additive into the biological protein-terylene composite powder; the functional additive comprises the following components: polyacrylamide, sorbitan monostearate, pentaerythritol; the addition amount of the functional additive is 20 percent of the biological protein powder; the functional additive comprises the following components in percentage by mass: 20: 35: 1.
(3) mixing and extruding
And (3) drying the graphene-terylene composite powder prepared in the step (1), the silk fibroin-terylene composite powder prepared in the step (2) and the polyester slice at the temperature of 120 ℃, and then, drying to ensure that the moisture content is below 20 ppm.
And then, uniformly mixing the mixture in a high-speed kneader, finally adding the mixture into a feeding bin of a double-screw extruder, mixing and extruding the mixture at a certain temperature, and then feeding the strips into a granulator for granulation to obtain the graphene-polyester composite master batch prepared by the invention.
In the graphene-terylene composite master batch, the addition amount of graphene relative to terylene polyester chips is 0.05%, and the addition amount of biological protein powder relative to terylene polyester chips is 2.5%.
The length-diameter ratio of the double-screw extruder is 40: 1, water-cooling and granulating at the main machine rotation speed of 150 Hz; wherein the extrusion temperature of each zone of the double-screw extruder is respectively as follows: 268 ℃, 278 ℃, 282 ℃, 285 ℃ and 278 ℃.
Feeding the prepared graphene-terylene composite master batch into a feeding bin, feeding the master batch into a spinning box through a screw extruder for spinning, then cooling and forming, dissolving and oiling the master batch through a slow cooling device and side air blowing, stretching the master batch through a pair of rollers I, a pair of rollers II and a pair of rollers III, and finally winding the master batch to prepare the graphene-terylene composite fiber.
Wherein the temperature of the spinning box is 270 ℃; the temperature of the slow cooling device is 245 ℃; the temperature of the side blowing device is 35 ℃, the humidity is 60 percent, and the wind speed is 0.3 m/s; the rotating speed of the oil tanker for oiling is 25 r/min; the temperatures of the first roller pair, the second roller pair and the third roller pair are respectively 75 ℃, 100 ℃ and 130 ℃.
The specific process of dissolution comprises:
firstly, placing the prepared graphene polyester fiber tows in a protease solution for enzyme treatment; in the protease solution, the enzyme treatment temperature is 55 ℃, and the enzyme treatment time is 30 min; then immersing the graphene polyester fiber tows subjected to enzyme treatment into a mixed solution of sodium bisulfite, guanidine hydrochloride and TCEP for treatment for 30 min; the temperature of the mixed solution is 85 ℃, the concentration of the sodium bisulfite in the mixed solution is 185g/L, and the concentration of the guanidine hydrochloride in the mixed solution is 160 g/L; the concentration of TCEP was 40 g/L.
Based on the graphene-terylene composite fiber prepared from the graphene-terylene composite master batch, the graphene-terylene composite fiber has good spinnability, soft hand feeling, and excellent antistatic property and antibacterial property.
Embodiment 3 a preparation method of a graphene-terylene composite master batch specifically comprises the following steps:
(1) preparation of graphene-terylene composite powder
The preparation method comprises the steps of taking polyester chips and spherical graphite with the mesh number of 120 as raw materials to prepare graphene oxide, and grinding and mixing the graphene oxide and the spherical graphite through mechanical ball milling to prepare graphene-polyester composite powder. Wherein the polyester chip has the intrinsic viscosity of 0.55-0.60dl/g, the terminal carboxyl content of 16-16.5mol/t, the diglycol content of 8.3-85 percent and the melting point of 245 ℃.
(2) Preparation of biological protein-terylene composite powder
And (3) grinding and mixing the wool protein powder and the polyester chips through mechanical ball milling to prepare the wool protein-polyester composite powder.
The adding amount of the biological protein powder is 4.5 percent of the mass of the polyester chips;
adding a functional additive into the biological protein-terylene composite powder; the functional additive comprises the following components: polyacrylamide, sorbitan monostearate, pentaerythritol; the addition amount of the functional additive is 10 percent of the biological protein powder; the functional additive comprises the following components in percentage by mass: 5: 20: 2.
(3) mixing and extruding
And (2) drying the graphene-polyester composite powder prepared in the step (1), the wool protein-polyester composite powder prepared in the step (2) and polyester chips at the temperature of 110 ℃, then drying until the moisture content is below 40ppm, then uniformly mixing in a high-speed kneading machine, finally adding into a feeding bin of a double-screw extruder, mixing and extruding at a certain temperature, and then feeding the strips into a granulator for granulation, thus obtaining the graphene-polyester composite master batch prepared by the invention.
In the graphene-polyester composite master batch, the addition amount of graphene relative to polyester chips is 2%, and the addition amount of biological protein powder relative to polyester chips is 2.0%.
The length-diameter ratio of the double-screw extruder is 40: 1, water-cooling and granulating at the main machine rotation speed of 150 Hz; wherein the extrusion temperature of each zone of the double-screw extruder is respectively as follows: 268 ℃, 278 ℃, 282 ℃, 285 ℃ and 278 ℃.
Feeding the prepared graphene-terylene composite master batch into a feeding bin, feeding the master batch into a spinning box through a screw extruder for spinning, then cooling and forming, dissolving and oiling the master batch through a slow cooling device and side air blowing, stretching the master batch through a pair of rollers I, a pair of rollers II and a pair of rollers III, and finally winding the master batch to prepare the graphene-terylene composite fiber.
Wherein the temperature of the spinning box is 260 ℃; the temperature of the slow cooling device is 255 ℃; the temperature of the side blowing device is 35 ℃, the humidity is 55%, and the wind speed is 0.3 m/s; the rotating speed of the oil tanker for oiling is 30 r/min; the temperatures of the first roller pair, the second roller pair and the third roller pair are respectively 70 ℃, 98 ℃ and 128 ℃.
The specific process of dissolution comprises:
firstly, placing the prepared graphene polyester fiber tows in a protease solution for enzyme treatment; in the protease solution, the enzyme treatment temperature is 55 ℃, and the enzyme treatment time is 30 min; then immersing the graphene polyester fiber tows subjected to enzyme treatment into a mixed solution of sodium bisulfite, guanidine hydrochloride and TCEP for treatment for 50 min; the temperature of the mixed solution is 75 ℃, the concentration of the sodium bisulfite in the mixed solution is 150g/L, and the concentration of the guanidine hydrochloride in the mixed solution is 180 g/L; the concentration of TCEP was 60 g/L.
Based on the method, the graphene-terylene composite fiber prepared from the graphene-terylene composite master batch has high strength and good spinnability, and the end breakage rate is reduced by 41-45%. Meanwhile, the fabric has soft hand feeling, the moisture absorption is up to more than 9% in the standard atmosphere with the relative humidity of 65%, and the fabric has excellent antistatic property and antibacterial property, and the specific detection indexes are shown in Table 1
TABLE 1
Comparative example 4
This example is substantially the same as the method of example 3, except that: in the preparation process of the bioprotein-terylene composite powder in the step (2), no component of the functional additive is added, and specific indexes of the prepared graphene-terylene composite fiber are shown in Table 2
TABLE 2
As can be seen from table 2, the fracture strength of the prepared graphene-polyester composite fiber prepared from the graphene-polyester composite masterbatch prepared by the comparative example is remarkably reduced after the functional additive is removed, and surprisingly, the electrical conductivity of the prepared graphene-polyester composite fiber is also remarkably reduced.
Unless otherwise specified, the proportions in the present invention are mass proportions, and the percentages are mass percentages.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The graphene-terylene composite master batch is characterized in that: in the graphene-terylene composite master batch, the content of graphene relative to terylene polyester chips is 0.05-2%, and the content of biological protein powder relative to terylene polyester chips is 1.5-4.5%;
the preparation method of the graphene polyester master batch comprises the following steps: the preparation method comprises the steps of graphene-terylene composite powder preparation, bioprotein-terylene composite powder preparation, mixing and extrusion; the extrusion adopts a double-screw extruder; the length-diameter ratio of the double-screw extruder is 40: 1, the rotating speed of the host is 120-150 Hz; the extrusion temperature of each zone of the double-screw extruder is respectively as follows: 268 ℃, 278 ℃, 282 ℃, 285 ℃ and 278 ℃;
the biological protein-terylene composite powder contains a functional additive; the functional additive comprises the following components: polyacrylamide, sorbitan monostearate, pentaerythritol; the addition amount of the functional additive is 10-30% of the biological protein powder; the functional additive comprises the following components in percentage by mass: 10-20%: 35-45%: 3 to 6 percent.
2. The graphene-terylene composite master batch according to claim 1, characterized in that: the graphene is graphene oxide; the graphene oxide is prepared from one or more of expandable graphite, natural crystalline flake graphite and spherical graphite.
3. The graphene-terylene composite master batch according to claim 1, characterized in that: the biological protein powder is one or more of wool protein powder and silk fibroin powder.
4. A method for preparing graphene-terylene composite fiber by using the graphene-terylene composite master batch of claim 1, which is characterized in that: the method comprises the following steps: feeding the prepared graphene-terylene composite master batch into a feeding bin, feeding the mixture into a spinning box through a screw extruder for spinning, then cooling, forming and oiling the mixture through a slow cooling device by cross air blow, stretching the mixture through a pair of rollers I, a pair of rollers II and a pair of rollers III, and finally winding the mixture to prepare graphene-terylene composite fiber; the temperature of the spinning box is 260-270 ℃; the temperature of the slow cooling device is 245-255 ℃; the temperature of the side blowing device is 35-40 ℃, the humidity is 55-60%, and the wind speed is 0.1-0.3 m/s.
5. The method for preparing graphene-terylene composite fibers from graphene-terylene composite master batches according to claim 4, wherein the method comprises the following steps: the rotating speed of the oil tanker for oiling is 25-30 r/min; the temperatures of the first roller pair, the second roller pair and the third roller pair are respectively 70-85 ℃, 95-100 ℃ and 125-135 ℃.
6. The method for preparing graphene-terylene composite fibers from graphene-terylene composite master batches according to claim 4, wherein the method comprises the following steps: after the cooling forming, a dissolving step is also included before oiling; firstly, putting the mixture into a protease solution for enzyme treatment; in the protease solution, the enzyme treatment temperature is 45-65 ℃, and the enzyme treatment time is 10-30 min.
7. The method for preparing graphene-terylene composite fibers from graphene-terylene composite master batches according to claim 6, wherein the method comprises the following steps: the dissolving step further comprises: immersing the graphene polyester fiber tows subjected to enzyme treatment in a mixed solution of sodium bisulfite, guanidine hydrochloride and TCEP for treatment for 30-50 min; the temperature of the mixed solution is 50-85 ℃, the concentration of the sodium bisulfite in the mixed solution is 185g/L, and the concentration of the guanidine hydrochloride in the mixed solution is 200 g/L; the concentration of TCEP is 30-60 g/L.
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| CN109796753A (en) * | 2019-01-24 | 2019-05-24 | 广州大学 | A kind of antistatic antibacterial fabric master batch and preparation method thereof |
| CN110406213B (en) * | 2019-07-18 | 2021-07-27 | 柯林(福建)服饰有限公司 | Method for manufacturing antistatic, antibacterial, far infrared, moisture-absorbing and quick-drying down fabric |
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| CN111155195B (en) * | 2019-12-31 | 2022-07-19 | 福建经纬新纤科技实业有限公司 | Production method of high-strength graphene-enhanced polyester staple fibers |
| CN111155199A (en) * | 2020-01-10 | 2020-05-15 | 特烯（厦门）科技有限公司 | Preparation method of graphene composite fiber |
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