CN114685859A - Modified conductive powder, conductive master batch, conductive fiber and preparation method thereof - Google Patents

Modified conductive powder, conductive master batch, conductive fiber and preparation method thereof Download PDF

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CN114685859A
CN114685859A CN202011635913.2A CN202011635913A CN114685859A CN 114685859 A CN114685859 A CN 114685859A CN 202011635913 A CN202011635913 A CN 202011635913A CN 114685859 A CN114685859 A CN 114685859A
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conductive
powder
master batch
commercially available
conductive powder
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CN114685859B (en
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唐晓峰
池玉玲
余子涯
逯琪
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Shanghai Langyi Functional Materials Co ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08K3/22—Oxides; Hydroxides of metals
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
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    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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Abstract

The invention discloses modified conductive powder, conductive master batch, conductive fiber and a preparation method thereof. The preparation method of the modified conductive powder comprises the following steps: and (3) reacting the metal oxide conductive powder with the mixed aqueous solution of the compatilizer, and drying. The conductive master batch comprises the following components: modified conductive powder and a polymer matrix. The conductive fiber comprises the following components: conductive master batch and polymer matrix. The modified conductive powder prepared by the invention has good dispersibility in a polymer matrix, and the prepared conductive fiber has low resistivity; the conductive powder in the conductive fiber is uniformly distributed and has long-acting durability; the conductive fiber of the invention has light fiber color and is easy to dye.

Description

Modified conductive powder, conductive master batch, conductive fiber and preparation method thereof
Technical Field
The invention relates to modified conductive powder, conductive master batch, conductive fiber and a preparation method thereof.
Background
The conductive fiber has a surface resistance of 10 under standard conditions (20 deg.C, 65% relative humidity)7A fiber having a length of not more than Ω · cm. The conductive fiber has good charge transmission capability, can eliminate static in a very short time, and is beneficial to processing and using fiber products. Besides antistatic property, the conductive fiber fabric also has the functions of conducting electricity, shielding electromagnetic waves and the like, and has wide application prospect in the aspects of intelligent wearable textiles, flexible electromagnetic shielding nets and the like.
Currently, conductive fibers can be classified into:
1) and conductive fibers with uniform components, such as metal conductive fibers, carbon fibers and the like. When the metal conductive fiber is used as a fabric, the hand feeling is poor, the cohesion is difficult, and the dyeing cannot be performed. Carbon fibers have low elongation at break and are not easy to process, and the application of the carbon fibers is limited by the black color of the carbon fibers.
2) Coating type conductive fiber: the conductivity of the fiber is related to the thickness and compactness of the surface conductive layer, and the conductive layer on the surface of the fiber can damage the conductive network of the surface to a certain extent under washing, friction, acid/alkali conditions and the like, so the conductivity durability of the fiber is poor. For example, chinese patent CN1584140A discloses a method for preparing conductive fiber by using conductive carbon black as a conductive component, dispersing the conductive carbon black in polyester through coating and dispersion treatment, extruding to obtain conductive master batch, and performing composite spinning. The conductive fiber is black in color, difficult to dye and poor in spinnability at high content.
3) Blend type conductive fiber: conductive fibers are prepared by dispersing a conductive filler in a polymer matrix and by solvent or melt spinning. The conductivity of the blend conductive fiber depends on the content of the filler, the dispersion effect, the processing method, the action type of the blend conductive fiber with the polymer matrix and the like. The conductive filler in the fiber is uniformly dispersed in the fiber and on the surface of the fiber, so the fiber has excellent conductive durability. Is the preparation method of the conductive fiber with the widest application range at present.
Disclosure of Invention
The invention aims to overcome the defects of poor dispersibility and functionality of conductive powder, and deep color and high resistivity of the prepared conductive fiber in the prior art, and provides modified conductive powder, conductive master batches, conductive fiber and preparation methods thereof.
The present invention solves the above technical problems by the following technical solutions.
The invention provides a preparation method of modified conductive powder, which comprises the following steps: reacting the metal oxide conductive powder with a mixed aqueous solution of a compatilizer, and drying to obtain the conductive powder;
wherein the addition amount of the compatilizer is 0.5 wt% to 5 wt%, for example 2 wt%; the addition amount of the compatilizer refers to the mass percentage of the compatilizer to the conductive powder; the reaction temperature is 50-80 ℃, for example 65 ℃.
In the invention, the metal oxide conductive powder can be conventional in the field; preferably one or more of antimony doped tin oxide (ATO), aluminium doped zinc oxide (AZO) and tin doped indium oxide (ITO).
Preferably, the antimony doped tin oxide (ATO) is commercially available from New materials of Hippocampus, Beijing, model number BY-TO1, and has a particle size of 100nm-200 nm.
Preferably, the aluminum-doped zinc oxide (AZO) is commercially available from New Xuancheng Crystal Material Co., Ltd, with a model of JR-AZO and a particle size of 200-300 nm.
Preferably, the tin-doped indium oxide (ITO) is commercially available from Anhui Ke Runzhi, Inc. under the model KR-ITO, and has a particle size of 300 nm.
In the invention, the particle size of the metal oxide conductive powder can be conventional in the field; preferably 100 to 500 nm.
In the present invention, the compatibilizer can be conventional in the art, and generally means the compatibilizer can improve the compatibility of the conductive powder with the polymer matrix; preferably one or more of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent; more preferably, the silane coupling agent is commercially available from Nanjing Haoyuan new material with the model number of KH 560; the titanate coupling agent is commercially available from Nanjing Jingtianwei chemical Co Ltd, and has model number of JTW-131; the aluminate coupling agent is commercially available from Jessica technologies, Inc. of Hangzhou, and has a model number of JXK-013.
In the present invention, it is known to those skilled in the art that the metal oxide conductive powder is uniformly mixed with the compatibilizer by ultrasonic dispersion.
Wherein, the time of ultrasonic dispersion is preferably 1 hour.
In the present invention, the reaction time may be conventional in the art; preferably 3 to 6 hours, such as 4.5 hours.
In the present invention, the drying operation may be conventional in the art, and is preferably filtration, washing and drying.
In one embodiment of the invention, the conductive powder is antimony-doped tin oxide, the addition amount of the conductive powder is 10g, the compatilizer is silane coupling agent KH560, the addition amount of the compatilizer is 0.05g, the time of ultrasonic dispersion is 1 hour, the volume of water in the mixed water solution is 500mL, the time of reaction is 3 hours, the temperature of reaction is 50 ℃, and the drying is drying after filtering and washing.
In another embodiment of the present invention, the conductive powder is tin-doped indium oxide, the addition amount of the conductive powder is 20g, the compatibilizer is a titanate coupling agent, the addition amount of the compatibilizer is 0.4g, the time of ultrasonic dispersion is 1 hour, the volume of water in the mixed aqueous solution is 500mL, the time of reaction is 4.5 hours, the temperature of reaction is 65 ℃, and the drying is drying after filtering and washing.
In another embodiment of the present invention, the conductive powder is aluminum-doped zinc oxide, the addition amount of the conductive powder is 30g, the compatibilizer is an aluminate coupling agent, the addition amount of the compatibilizer is 1.5g, the time of ultrasonic dispersion is 1 hour, the volume of water in the mixed aqueous solution is 500mL, the time of reaction is 6 hours, the temperature of reaction is 80 ℃, and the drying is drying after filtering and washing.
The invention provides modified conductive powder prepared by the preparation method of the modified conductive powder.
The invention provides a conductive master batch, which comprises the following components: the modified conductive powder, the dispersant and the polymer matrix;
wherein the addition amount of the modified conductive powder is 40-60 wt%, for example 50 wt%; the addition amount of the dispersant is 1 wt% to 3 wt%, for example, 2 wt%; the addition amount of the modified conductive powder is the mass percentage of the modified conductive powder in the total mass of the polymer matrix and the modified conductive powder; the addition amount of the dispersing agent is the percentage of the mass of the dispersing agent in the total mass of the polymer matrix and the modified conductive powder.
In the invention, the dispersant can be conventional in the field and generally refers to a functional auxiliary agent capable of promoting the modified conductive powder to disperse in a polymer matrix; preferably a polyester wax; more preferably, the polyester wax is commercially available from Shanghai Kaiyn chemical Co., Ltd, model No. WE 4.
Preferably, the conductive master batch further comprises an antioxidant; more preferably, the antioxidant is added in an amount of 0.2 wt% to1 wt%, for example, 0.5 wt%.
Wherein, the antioxidant can be conventional in the field, and generally refers to an auxiliary agent capable of reducing the oxidative degradation of macromolecules; preferably 1010 antioxidant or DLTP antioxidant; more preferably, the 1010 antioxidant is commercially available from Shanghai Lier New materials, Inc. under the model LENOX 1010; the DLTP antioxidant is commercially available from Nanjing Basider chemical Co., Ltd, and has the model of BSD-DLTP.
Preferably, the conductive master batch further comprises a delustering agent; more preferably, the matting agent is added in an amount of 1 to 5 wt%, for example 2 wt%.
The matting agent can be a conventional matting agent and generally refers to nano-scale powder capable of improving the visible light scattering ability of the fiber surface; preferably one or more of titanium dioxide, silicon dioxide and zinc oxide; more preferably the titanium dioxide is commercially available from Nanjing titanium dioxide chemical Co., Ltd, model No. NR 930; the silica is commercially available from degussa chemical ltd under the model number R974; the zinc oxide is commercially available from bofu technologies under model number S40.
The addition amount of the antioxidant or the delustering agent in the invention is the percentage of the total mass of the polymer matrix and the modified conductive powder.
In the present invention, the polymer matrix may be conventional in the art, and refers to a polymer capable of forming fibers; preferably a polyester-based polymer matrix or a polyamide-based polymer matrix.
Wherein the polyester-based polymer matrix may be conventional in the art, such as PET, PBT or PTT; preferably PET; more preferably, the PET is commercially available from Shanghai Yunwan, as CB602, and has a viscosity of 0.8 dL/g.
Wherein, the polyamide-based polymer matrix can be conventional in the field, such as PA6, PA 66; preferably PA 6; more preferably, the PA6 is commercially available from Zhejiang golden color New materials, Inc., model number M2400, and has a viscosity of 2.47 dL/g.
Preferably, the polymer matrix is in a powder form, such as PET powder or PA6 powder.
In the present invention, it is known to those skilled in the art that the polymer matrix needs to be dried before use, and the drying operation of the polymer matrix can be conventional in the art.
Preferably, the drying temperature of the polymer matrix of the conductive masterbatch is 80-140 ℃, for example, 90 ℃, 100 ℃ or 120 ℃.
Preferably, the drying time of the polymer matrix of the conductive masterbatch is 4-12 hours, such as 4 hours, 6 hours or 8 hours.
The invention provides a preparation method of conductive master batches, which comprises the following steps: mixing the components of the conductive master batch and extruding.
In the present invention, the skilled person knows that the extrusion is generally performed by twin-screw melt extrusion, and the extrusion temperature is 200 to 270 ℃, for example 240 to 270 ℃ or 200 to 230 ℃.
In one embodiment of the invention, the polymer matrix is PET powder, the addition amount of the polymer matrix is 240g, the drying temperature of the polymer matrix is 140 ℃, the drying time of the polymer matrix is 4 hours, the addition amount of the modified conductive powder is 160g, the antioxidant is 1010 antioxidant, the addition amount of the antioxidant is 0.48g, the dispersant is polyester wax dispersant, the addition amount of the dispersant is 2.4g, the delustering agent is titanium dioxide, the addition amount of the delustering agent is 2.4g, the conductive master batch is extruded by the double-screw extruder, and the extrusion temperature is 240-270 ℃.
In another embodiment of the invention, the polymer matrix is PET powder, the addition amount of the polymer matrix is 200g, the drying temperature of the polymer matrix is 120 ℃, the drying time of the polymer matrix is 6 hours, the addition amount of the modified conductive powder is 200g, the antioxidant is 1010 antioxidant, the addition amount of the antioxidant is 1g, the dispersant is polyester wax dispersant, the addition amount of the dispersant is 4g, the matting agent is silicon dioxide, the addition amount of the matting agent is 4g, the conductive master batch is extruded by the twin-screw extruder, and the extrusion temperature is 240-270 ℃.
In another embodiment of the invention, the polymer matrix is PET powder, the addition amount of the polymer matrix is 160g, the drying temperature of the polymer matrix is 100 ℃, the drying time of the polymer matrix is 8 hours, the addition amount of the modified conductive powder is 240g, the antioxidant is 1010 antioxidant, the addition amount of the antioxidant is 1.6g, the dispersant is polyester wax dispersant, the addition amount of the dispersant is 4.8g, the delustering agent is zinc oxide, the addition amount of the delustering agent is 8g, the conductive master batch is extruded by the twin-screw extruder, and the extrusion temperature is 240-270 ℃.
In another embodiment of the invention, the polymer matrix is PA6 powder, the addition amount of the polymer matrix is 240g, the drying temperature of the polymer matrix is 80 ℃, the drying time of the polymer matrix is 8 hours, the addition amount of the modified conductive powder is 160g, the antioxidant is DLTP antioxidant, the addition amount of the antioxidant is 0.48g, the dispersant is polyester wax dispersant, the addition amount of the dispersant is 2.4g, the delustering agent is titanium dioxide, the addition amount of the delustering agent is 2.4g, the conductive master batch is extruded by the twin-screw extruder, and the extrusion temperature is 200-230 ℃.
In another embodiment of the invention, the polymer matrix is PA6 powder, the addition amount of the polymer matrix is 200g, the drying temperature of the polymer matrix is 90 ℃, the drying time of the polymer matrix is 6 hours, the addition amount of the modified conductive powder is 200g, the antioxidant is 1010 antioxidant, the addition amount of the antioxidant is 1g, the dispersant is polyester wax dispersant, the addition amount of the dispersant is 4g, the delustering agent is silicon dioxide, the addition amount of the delustering agent is 4g, the conductive master batch is extruded by the twin-screw extruder, and the extrusion temperature is 200-230 ℃.
In another embodiment of the invention, the polymer matrix is PA6 powder, the addition amount of the polymer matrix is 160g, the drying temperature of the polymer matrix is 100 ℃, the drying time of the polymer matrix is 4 hours, the addition amount of the modified conductive powder is 240g, the antioxidant is 1010 antioxidant, the addition amount of the antioxidant is 1.6g, the dispersant is polyester wax dispersant, the addition amount of the dispersant is 4.8g, the delustering agent is zinc oxide, the addition amount of the delustering agent is 8g, the conductive master batch is extruded by the twin-screw extruder, and the extrusion temperature is 200-230 ℃.
The invention provides a conductive fiber, which comprises the following components: the conductive master batch and the polymer carrier;
wherein the addition amount of the conductive master batch is 8-25 wt%; the addition amount of the conductive master batch is the percentage of the mass of the conductive master batch in the total mass of the conductive master batch and the polymer carrier.
In the present invention, the polymer carrier may be conventional in the art, and refers to a polymer capable of forming fibers; preferably a polyester polymer carrier or a polyamide polymer carrier.
Wherein the polyester-based polymeric carrier may be conventional in the art, such as PET, PBT or PTT; preferably PET; more preferably, the PET is commercially available from Shanghai Yunwan, as CB602, and has a viscosity of 0.8 dL/g.
Wherein, the polyamide-based polymer carrier can be conventional in the field, such as PA6, PA 66; preferably PA 6; more preferably, the PA6 is commercially available from Zhejiang golden color New materials, Inc., model number M2400, and has a viscosity of 2.47 dL/g.
In the present invention, the polymer matrix and the polymer carrier may be the same.
Preferably, the drying temperature of the polymer carrier is 90-140 ℃.
Preferably, the drying time of the polymer carrier is 8 to 12 hours, such as 10 hours.
The invention provides a preparation method of conductive fibers, which comprises the following steps: and (3) blending the components of the conductive fiber, and carrying out melt spinning.
Preferably, the polymer carrier slice is blended with the conductive master batch.
In the present invention, the melt spinning may be performed using a twin screw extruder as is conventional in the art.
In the present invention, the temperature of the melt spinning may be conventional in the art; preferably 240 to 290 ℃.
Preferably, the temperature of each heating cylinder of the twin-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in this order or 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in this order.
In the present invention, the speed of the melt spinning may be conventional in the art; preferably 1000 to 3000m/min, such as 2000 m/min.
In one embodiment of the invention, the addition amount of the conductive master batch is 100g, the polymer carrier is PET, the addition amount of the polymer carrier is 400g, the drying temperature of the polymer carrier is 140 ℃, the drying time of the polymer carrier is 12 hours, the polymer carrier is sliced and then blended with the conductive master batch, a double-screw extruder is adopted for melt spinning, the temperature of each heating cylinder of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the speed of the melt spinning is 1000 m/min.
In another embodiment of the present invention, the addition amount of the conductive masterbatch is 150g, the polymer carrier is PET, the addition amount of the polymer carrier is 350g, the drying temperature of the polymer carrier is 140 ℃, the drying time of the polymer carrier is 10 hours, the polymer carrier is sliced and then blended with the conductive masterbatch, a twin-screw extruder is adopted to melt-spin, the temperature of each heating cylinder of the twin-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the speed of the melt-spinning is 2000 m/min.
In another embodiment of the present invention, the addition amount of the conductive masterbatch is 208g, the polymer carrier is PET, the addition amount of the polymer carrier is 292g, the drying temperature of the polymer carrier is 140 ℃, the drying time of the polymer carrier is 8 hours, the polymer carrier is sliced and then blended with the conductive masterbatch, a twin-screw extruder is adopted to melt-spin, the temperature of each heating cylinder of the twin-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the speed of the melt-spinning is 3000 m/min.
In another embodiment of the present invention, the addition amount of the conductive masterbatch is 100g, the polymeric carrier is PA6, the addition amount of the polymeric carrier is 400g, the drying temperature of the polymeric carrier is 90 ℃, the drying time of the polymeric carrier is 12 hours, the polymeric carrier is sliced and then blended with the conductive masterbatch, a twin-screw extruder is adopted to melt-spin, the temperature of each heating cylinder of the twin-screw extruder is 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in sequence, and the speed of the melt-spinning is 1000 m/min.
In another embodiment of the present invention, the addition amount of the conductive masterbatch is 150g, the polymer carrier is PET, the addition amount of the polymer carrier is 350g, the drying temperature of the polymer carrier is 90 ℃, the drying time of the polymer carrier is 10 hours, the polymer carrier is sliced and then blended with the conductive masterbatch, a twin-screw extruder is adopted to melt-spin, the temperature of each heating cylinder of the twin-screw extruder is 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in sequence, and the speed of the melt-spinning is 2000 m/min.
In another embodiment of the present invention, the addition amount of the conductive masterbatch is 208g, the polymer carrier is PA6, the addition amount of the polymer carrier is 292g, the drying temperature of the polymer carrier is 90 ℃, the drying time of the polymer carrier is 8 hours, the polymer carrier is sliced and then blended with the conductive masterbatch, a twin-screw extruder is adopted to melt-spin, the temperature of each heating cylinder of the twin-screw extruder is 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in sequence, and the speed of the melt-spinning is 3000 m/min.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
1. the modified conductive powder has good dispersibility in a polymer matrix, and the prepared conductive fiber has low resistivity.
2. The conductive powder in the conductive fiber is uniformly distributed and has long-acting durability.
3. The conductive fiber of the invention has light fiber color and is easy to dye.
Drawings
FIG. 1 shows a modified conductive powder prepared in example 1 of the present invention.
Fig. 2 shows the conductive masterbatch prepared in example 1 of the present invention.
Fig. 3 is a conductive fiber prepared in example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In each of the following examples, the resistivity of the conductive fiber is measured by a fiber specific resistance measuring instrument under an environment of a temperature of 25 ℃ and a humidity of 60 wt%.
In each of the following examples, antimony doped tin oxide (ATO) was commercially available from New materials, Inc., of high science, Boyu, Beijing, model number BY-TO1, having a particle size of 100nm TO 200 nm; aluminum-doped zinc oxide (AZO) is commercially available from New Material of Xuancheng Jingrui, Inc., type JR-AZO, particle size 200-; tin-doped indium oxide (ITO) is commercially available from Anhui Ke run nanometer technology, Inc., with a model of KR-ITO and a particle size of 300 nm;
the silane coupling agent is commercially available from Nanjing Haoyuan new material, and has the model number of KH 560; the titanate coupling agent is commercially available from Nanjing Jingtianwei chemical Co Ltd, and has model number of JTW-131; the aluminate coupling agent is commercially available from Jessiccard technologies, Inc. of Hangzhou, and has a model number of JXK-013;
the polyester wax is commercially available from Kyon chemical Co., Ltd, Shanghai, under model number WE 4;
antioxidant 1010 is commercially available from Shanghai Lier New materials, Inc. with model number LENOX 1010; antioxidant DLTP was purchased from Nanjing Basdide chemical Co., Ltd, and its model number is BSD-DLTP;
titanium dioxide is commercially available from Nanjing titanium dioxide chemical Co., Ltd, and has the model number of NR 930; silica is commercially available from degussa chemical ltd under model number R974; zinc oxide is commercially available from bofu science and technology with model number S40;
PET is commercially available from Shanghai Yuanshu, has a model of CB602 and a viscosity of 0.8 dL/g; PA6 was purchased from Zhejiang golden New materials, Inc. with a model number of M2400 and a viscosity of 2.47 dL/g.
Example 1
(1) Modified conductive powder
Dispersing 10g of ATO conductive powder into 500mL of deionized water by ultrasonic wave for 1 hour, adding 0.05g of silane coupling agent KH560, stirring and reacting for 3 hours at 50 ℃, filtering, washing and drying to obtain the modified conductive powder, wherein the formula is shown in figure 1.
(2) Conductive masterbatch
After 240g of PET powder dried at 140 ℃ for 4 hours, 160g of modified conductive powder, 0.48g of 1010 antioxidant, 2.4g of polyester wax dispersant and 2.4g of titanium dioxide matting agent are uniformly mixed, all temperature ranges of the twin screws are adjusted to be 240-270 ℃ for blending and extrusion, and the conductive master batch is obtained, as shown in figure 2.
(3) Conductive fiber
Uniformly blending 100g of conductive master batch and 400g of PET slices dried for 12 hours at 140 ℃, and carrying out melt spinning by adopting a double-screw extruder; wherein the temperature of each heating cylinder of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the speed of melt spinning is 1000 m/min; thus obtaining the conductive fiber, as shown in fig. 3.
Testing the resistivity of the conductive fiber at 25 deg.C and 60 wt% with a fiber specific resistance tester, wherein the resistivity is 2.1 × 105Ωcm。
Comparative example 1
(1) Conductive masterbatch
Uniformly mixing 240g of PET powder dried for 4 hours at 140 ℃, 160g of ATO conductive powder, 0.48g of 1010 antioxidant, 2.4g of polyester wax dispersant and 2.4g of titanium dioxide delustering agent, adjusting each temperature interval of the twin screws to be 240-270 ℃, and blending and extruding to obtain the conductive master batch.
(2) Conductive fiber
Uniformly blending 100g of conductive master batch and 400g of PET slices dried for 12 hours at 140 ℃, and carrying out melt spinning by adopting a double-screw extruder; wherein the temperature of each heating cylinder of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the speed of melt spinning is 1000 m/min; thus obtaining the conductive fiber.
Testing the resistivity of the conductive fiber at 25 deg.C and 60 wt% with a fiber specific resistance tester, wherein the resistivity is 5.7 × 107Ωcm。
Example 2
(1) Modified conductive powder
Dispersing 20g of ITO conductive powder into 500mL of deionized water by 1 hour of ultrasonic wave, adding 0.4g of titanate coupling agent, stirring and reacting for 4.5 hours at 65 ℃, filtering, washing and drying to obtain the modified conductive powder.
(2) Conductive masterbatch
200g of PET powder dried for 6 hours at 120 ℃, 200g of modified conductive powder, 1g of 1010 antioxidant, 4g of polyester wax dispersant and 4g of silicon dioxide delustering agent are uniformly mixed, and then the temperature ranges of the double screws are adjusted to be 240-270 ℃ for blending and extrusion, so that the conductive master batch is obtained.
(3) Conductive fiber
Uniformly blending 150g of conductive master batch and 350g of PET slices dried for 10 hours at 140 ℃, and carrying out melt spinning by adopting a double-screw extruder; wherein the temperature of each heating cylinder of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the speed of melt spinning is 2000 m/min; thus obtaining the conductive fiber.
Testing the resistivity of the conductive fiber at 25 deg.C and 60 wt% with a fiber specific resistance tester, wherein the resistivity is 1.6 × 105Ωcm。
Comparative example 2
(1) Modified conductive powder
Dispersing 20g of ITO conductive powder into 500mL of deionized water by 1 hour of ultrasonic wave, adding 0.4g of titanate coupling agent, stirring and reacting for 4.5 hours at 65 ℃, filtering, washing and drying to obtain the modified conductive powder.
(2) Conductive masterbatch
200g of PET powder dried for 6 hours at 120 ℃, 200g of modified conductive powder, 1g of 1010 antioxidant and 4g of silica matting agent are uniformly mixed, and then the temperature ranges of the double screws are adjusted to be 240-270 ℃ for blending and extrusion, so that the conductive master batch is obtained.
(3) Conductive fiber
Uniformly blending 150g of conductive master batch and 350g of PET slices dried for 10 hours at 140 ℃, and carrying out melt spinning by adopting a double-screw extruder; wherein the temperature of each heating cylinder of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the speed of melt spinning is 2000 m/min; thus obtaining the conductive fiber.
Testing the resistivity of the conductive fiber at 25 deg.C and 60 wt% with a fiber specific resistance tester, wherein the resistivity is 3.6 × 108Ωcm。
Example 3
(1) Modified conductive powder
And (3) ultrasonically dispersing 30g of AZO conductive powder into 500mL of deionized water for 1 hour, adding 1.5g of aluminate coupling agent, stirring and reacting for 6 hours at 80 ℃, filtering, washing and drying to obtain the modified conductive powder.
(2) Conductive masterbatch
160g of PET powder dried for 8 hours at 100 ℃, 240g of modified conductive powder, 1.6g of 1010 antioxidant, 4.8g of polyester wax dispersant and 8g of zinc oxide delustering agent are uniformly mixed, and then the temperature ranges of the double screws are adjusted to be 240-270 ℃ for blending and extrusion, so that the conductive master batch is obtained.
(3) Conductive fiber
Uniformly blending 208g of conductive master batch and 292g of PET slices dried for 8 hours at 140 ℃, and carrying out melt spinning by adopting a double-screw extruder; wherein the temperature of each heating cylinder of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the speed of melt spinning is 3000 m/min; thus obtaining the conductive fiber.
Testing the resistivity of the conductive fiber at 25 deg.C and 60 wt% with a fiber specific resistance tester, wherein the resistivity is 3.2 × 105Ωcm。
Comparative example 3
(1) Conductive masterbatch
160g of PET powder dried for 8 hours at 100 ℃, 240g of AZO conductive powder, 1.6g of 1010 antioxidant and 8g of zinc oxide delustering agent are uniformly mixed, and then the temperature ranges of the double screws are adjusted to be 240-270 ℃ for blending and extrusion, so that the conductive master batch is obtained.
(2) Conductive fiber
Uniformly blending 208g of conductive master batch and 292g of PET slices dried for 8 hours at 140 ℃, and carrying out melt spinning by adopting a double-screw extruder; wherein the temperature of each heating cylinder of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the speed of melt spinning is 3000 m/min; thus obtaining the conductive fiber.
Testing the resistivity of the conductive fiber at 25 deg.C and 60 wt% with a fiber specific resistance tester, wherein the resistivity is 7.6 × 108Ωcm。
Example 4
(1) Modified conductive powder
Dispersing 10g of ATO conductive powder into 500mL of deionized water by ultrasonic for 1 hour, adding 0.05g of silane coupling agent KH560, stirring and reacting for 3 hours at 50 ℃, filtering, washing and drying to obtain the modified conductive powder.
(2) Conductive masterbatch
240g of PA6 powder dried for 8 hours at the temperature of 80 ℃, 160g of modified conductive powder, 0.48g of DLTP antioxidant, 2.4g of polyester wax dispersant and 2.4g of titanium dioxide delustering agent are uniformly mixed, and then the temperature ranges of the twin screws are adjusted to be between 200 ℃ and 230 ℃ for blending and extrusion, so that the conductive master batch is obtained.
(3) Conductive fiber
Uniformly blending 100g of conductive master batch and 400g of PA6 chips dried at 90 ℃ for 12 hours, and carrying out melt spinning by adopting a double-screw extruder; wherein the temperature of each heating cylinder of the double-screw extruder is 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in sequence, and the speed of melt spinning is 1000 m/min; thus obtaining the conductive fiber.
Testing the resistivity of the conductive fiber at 25 deg.C and 60 wt% with a fiber specific resistance tester, wherein the resistivity is 3.8 × 104Ωcm。
Comparative example 4
(1) Conductive masterbatch
240g of PA6 powder dried for 8 hours at 80 ℃, 160g of ATO conductive powder, 0.48g of DLTP antioxidant, 2.4g of polyester wax dispersant and 2.4g of titanium dioxide delustering agent are mixed uniformly, and then the temperature ranges of the twin screws are adjusted to be between 200 ℃ and 230 ℃ for blending and extrusion, so that the conductive master batch is obtained.
(2) Conductive fiber
Uniformly blending 100g of conductive master batch and 400g of PA6 chips dried at 90 ℃ for 12 hours, and carrying out melt spinning by adopting a double-screw extruder; wherein the temperature of each heating cylinder of the double-screw extruder is 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in sequence, and the speed of melt spinning is 1000 m/min; thus obtaining the conductive fiber.
Testing the resistivity of the conductive fiber at 25 deg.C and 60 wt% with a fiber specific resistance tester, wherein the resistivity is 3.5 × 107Ωcm。
Example 5
(1) Modified conductive powder
Dispersing 20g of ITO conductive powder into 500mL of deionized water by 1 hour of ultrasonic wave, adding 0.4g of titanate coupling agent, stirring and reacting for 4.5 hours at 65 ℃, filtering, washing and drying to obtain the modified conductive powder.
(2) Conductive masterbatch
200g of PA6 powder dried for 6 hours at 90 ℃, 200g of modified conductive powder, 1g of 1010 antioxidant, 4g of polyester wax dispersant and 4g of silicon dioxide delustering agent are uniformly mixed, and then the mixture is blended and extruded at 200-230 ℃ by adjusting each temperature interval of the twin screws, so as to obtain the conductive master batch.
(3) Conductive fiber
Uniformly blending 150g of conductive master batch and 350g of PA6 chips dried for 10 hours at 90 ℃, and carrying out melt spinning by adopting a double-screw extruder; wherein the temperature of each heating cylinder of the double-screw extruder is 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in sequence, and the speed of melt spinning is 2000 m/min; thus obtaining the conductive fiber.
Testing the resistivity of the conductive fiber at 25 deg.C and 60 wt% with a fiber specific resistance tester, wherein the resistivity is 4.2 × 104Ωcm。
Comparative example 5
(1) Modified conductive powder
Dispersing 20g of ITO conductive powder into 500mL of deionized water by 1 hour of ultrasonic wave, adding 0.4g of titanate coupling agent, stirring and reacting for 4.5 hours at 65 ℃, filtering, washing and drying to obtain the modified conductive powder.
(2) Conductive masterbatch
200g of PA6 powder which is dried for 6 hours at 90 ℃, 200g of modified conductive powder, 1g of 1010 antioxidant and 4g of silicon dioxide flatting agent are uniformly mixed, and then all temperature ranges of the double screws are adjusted to be between 200 ℃ and 230 ℃ for blending and extrusion, so that the conductive master batch is obtained.
(3) Conductive fiber
Uniformly blending 150g of conductive master batch and 350g of PA6 chips dried for 10 hours at 90 ℃, and carrying out melt spinning by adopting a double-screw extruder; wherein the temperature of each heating cylinder of the double-screw extruder is 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in sequence, and the speed of melt spinning is 2000 m/min; thus obtaining the conductive fiber.
Testing the resistivity of the conductive fiber at 25 deg.C and 60 wt% with a fiber specific resistance tester, wherein the resistivity is 7.5 × 107Ωcm。
Example 6
(1) Modified conductive powder
And ultrasonically dispersing 30g of AZO conductive powder in 500mL of deionized water for 1 hour, adding 1.5g of aluminate coupling agent, stirring and reacting at 80 ℃ for 6 hours, filtering, washing and drying to obtain the modified conductive powder.
(2) Conductive masterbatch
160g of PA6 powder dried for 4 hours at 100 ℃, 240g of modified conductive powder, 1.6g of 1010 antioxidant, 4.8g of polyester wax dispersant and 8g of zinc oxide delustering agent are uniformly mixed, and then the temperature ranges of the twin screws are adjusted to be between 200 ℃ and 230 ℃ for blending and extrusion, so that the conductive master batch is obtained.
(3) Conductive fiber
Uniformly blending 208g of conductive master batch and 292g of PA6 chips dried at 90 ℃ for 8 hours, and carrying out melt spinning by adopting a double-screw extruder; wherein the temperature of each heating cylinder of the double-screw extruder is 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in sequence, and the speed of melt spinning is 3000 m/min; thus obtaining the conductive fiber.
Testing the resistivity of the conductive fiber at 25 deg.C and 60 wt% with a fiber specific resistance tester, wherein the resistivity is 3.4 × 104Ωcm。
Comparative example 6
(1) Conductive masterbatch
160g of PA6 powder dried for 4 hours at 100 ℃, 240g of modified conductive powder, 1.6g of 1010 antioxidant and 8g of zinc oxide delustering agent are uniformly mixed, and then the mixture is blended and extruded at 200-230 ℃ by adjusting each temperature interval of the twin screws, so as to obtain the conductive master batch.
(2) Conductive fiber
Uniformly blending 208g of conductive master batch and 292g of PA6 chips dried at 90 ℃ for 8 hours, and carrying out melt spinning by adopting a double-screw extruder; wherein the temperature of each heating cylinder of the double-screw extruder is 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in sequence, and the speed of melt spinning is 3000 m/min; thus obtaining the conductive fiber.
Testing the resistivity of the conductive fiber at 25 deg.C and 60 wt% with a fiber specific resistance tester, wherein the resistivity is 5.9 × 108Ωcm。
Comparative example 7
(1) Modified conductive powder
Dispersing 10g of ATO conductive powder into 500mL of deionized water by ultrasonic for 1 hour, adding 0.01g of silane coupling agent KH560, stirring and reacting for 3 hours at 50 ℃, filtering, washing and drying to obtain the modified conductive powder.
(2) Conductive masterbatch
Uniformly mixing 240g of PET powder dried for 4 hours at 140 ℃, 160g of modified conductive powder, 0.48g of 1010 antioxidant, 2.4g of polyester wax dispersant and 2.4g of titanium dioxide delustering agent, adjusting each temperature interval of the twin-screw to be 240-270 ℃, and blending and extruding to obtain the conductive master batch.
(3) Conductive fiber
Uniformly blending 100g of conductive master batch and 400g of PET slices dried for 12 hours at 140 ℃, and carrying out melt spinning by adopting a double-screw extruder; wherein the temperature of each heating cylinder of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the speed of melt spinning is 1000 m/min; thus obtaining the conductive fiber.
Testing the resistance of the conductive fiber at 25 deg.C and 60 wt% with fiber specific resistance testerRate of resistivity of 2.5X 109Ωcm。
Comparative example 8
(1) Modified conductive powder
Dispersing 20g of ITO conductive powder into 500mL of deionized water by 1 hour of ultrasonic wave, adding 2g of titanate coupling agent, stirring and reacting for 4.5 hours at 65 ℃, filtering, washing and drying to obtain the modified conductive powder.
(2) Conductive masterbatch
200g of PET powder dried for 6 hours at 120 ℃, 200g of modified conductive powder, 1g of 1010 antioxidant, 4g of polyester wax dispersant and 4g of silicon dioxide delustering agent are uniformly mixed, and then the temperature ranges of the double screws are adjusted to be 240-270 ℃ for blending and extrusion, so that the conductive master batch is obtained.
(3) Conductive fiber
Uniformly blending 150g of conductive master batch and 350g of PET slices dried for 10 hours at 140 ℃, and carrying out melt spinning by adopting a double-screw extruder; wherein the temperature of each heating cylinder of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the speed of melt spinning is 2000 m/min; thus obtaining the conductive fiber.
Testing the resistivity of the conductive fiber at 25 deg.C and 60 wt% with a fiber specific resistance tester, wherein the resistivity is 3.7 × 109Ωcm。
Comparative example 9
(1) Modified conductive powder
And (3) ultrasonically dispersing 30g of AZO conductive powder into 500mL of deionized water for 1 hour, adding 1.5g of aluminate coupling agent, stirring at room temperature for reacting for 6 hours, filtering, washing and drying to obtain the modified conductive powder.
(2) Conductive masterbatch
160g of PET powder dried for 8 hours at 100 ℃, 240g of modified conductive powder, 1.6g of 1010 antioxidant, 4.8g of polyester wax dispersant and 8g of zinc oxide delustering agent are uniformly mixed, and then the temperature ranges of the double screws are adjusted to be 240-270 ℃ for blending and extrusion, so that the conductive master batch is obtained.
(3) Conductive fiber
Uniformly blending 208g of conductive master batch and 292g of PET slices dried for 8 hours at 140 ℃, and carrying out melt spinning by adopting a double-screw extruder; wherein the temperatures of all heating cylinder bodies of the double-screw extruder are 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the speed of melt spinning is 3000 m/min; thus obtaining the conductive fiber.
Testing the resistivity of the conductive fiber at 25 deg.C and 60 wt% with a fiber specific resistance tester, wherein the resistivity is 5.6 × 108Ωcm。
Comparative example 10
(1) Modified conductive powder
Dispersing 10g of ATO conductive powder into 500mL of acetone by ultrasonic for 1 hour, adding 0.05g of silane coupling agent KH560, stirring and reacting for 3 hours at 50 ℃, filtering, washing and drying to obtain the modified conductive powder.
(2) Conductive masterbatch
Uniformly mixing 240g of PET powder dried for 4 hours at 140 ℃, 160g of modified conductive powder, 0.48g of 1010 antioxidant, 2.4g of polyester wax dispersant and 2.4g of titanium dioxide delustering agent, adjusting each temperature interval of the twin-screw to be 240-270 ℃, and blending and extruding to obtain the conductive master batch.
(3) Conductive fiber
Uniformly blending 100g of conductive master batch and 400g of PET slices dried for 12 hours at 140 ℃, and carrying out melt spinning by adopting a double-screw extruder; wherein the temperature of each heating cylinder of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the speed of melt spinning is 1000 m/min; thus obtaining the conductive fiber.
Testing the resistivity of the conductive fiber at 25 deg.C and 60 wt% with a fiber specific resistance tester, wherein the resistivity is 5.4 × 109Ωcm。
Effect example 1
The conductive fibers prepared in examples 1 to 6 and comparative examples 1 to 9 were subjected to a color model test, and the test results are shown in table 1.
The Lab color model in the embodiment of the effect is disclosed in the national standard GB/T7921-2008, L refers to brightness, and a and b are two color channels. Wherein, the colors included in a are from dark green (low brightness value) to gray (medium brightness value) to bright pink red (high brightness value); b is from bright blue (low brightness value) to gray (medium brightness value) to yellow (high brightness value). Therefore, the value of b can reflect the shade of the color of the conductive fiber prepared.
In addition, Table 1 summarizes the specific resistance data of the conductive fibers prepared in examples 1-6 and comparative examples 1-10.
TABLE 1
Figure BDA0002881103070000191
Figure BDA0002881103070000201
As can be seen from Table 1, the conductive fibers prepared in examples 1 to 6 of the present invention have better conductive properties than those of comparative examples 1 to 10, and the conductive fibers prepared in examples 1 to 6 have lighter colors. While comparative examples 1 and 4, comparative examples 2 and 5, comparative examples 3 and 6, comparative example 7, comparative example 8, comparative example 9, in which the conductive powder and the compatibilizing agent were reacted at room temperature, and comparative example 10, in which acetone was used as a reaction system, resulted in an increase in the specific resistance and a darkening in the color of the conductive fiber produced.

Claims (10)

1. A preparation method of modified conductive powder is characterized by comprising the following steps: reacting the metal oxide conductive powder with a mixed aqueous solution of a compatilizer, and drying to obtain the conductive powder;
wherein the addition amount of the compatilizer is 0.5-5 wt%; the addition amount of the compatilizer refers to the mass percentage of the compatilizer to the conductive powder; the reaction temperature is 50-80 ℃.
2. The method of claim 1, wherein the metal oxide conductive powder is one or more of antimony doped tin oxide, aluminum doped zinc oxide, and tin doped indium oxide;
and/or the particle size of the metal oxide conductive powder is 100-500 nm;
and/or the addition amount of the compatilizer is 2 wt%;
and/or the compatilizer is one or more of silane coupling agent, titanate coupling agent and aluminate coupling agent;
and/or uniformly mixing the metal oxide conductive powder with the compatilizer through ultrasonic dispersion;
and/or the reaction time is 3-6 hours, such as 4.5 hours;
and/or the temperature of the reaction is 65 ℃;
and/or the drying operation is filtering, washing and drying.
3. The method of claim 2, wherein the antimony doped tin oxide is commercially available from new materials of gagagaku, beijing, model BY-TO1, and has a particle size of 100nm TO 200 nm;
and/or the aluminum-doped zinc oxide is commercially available from New Material of Xuancheng Jingrui, Inc., with the model of JR-AZO and the particle size of 200-300 nm;
and/or the tin-doped indium oxide is commercially available from Anhui Kerun nanotechnology Co., Ltd, has the model of KR-ITO and the particle size of 300 nm;
and/or the silane coupling agent is commercially available from a new material of Nanjing Haoyuan, and has the model number of KH 560;
and/or the titanate coupling agent is purchased from Nanjing warp Tian Rev chemical Co., Ltd, and the model is JTW-131;
and/or the aluminate coupling agent is commercially available from Jeccard technologies, Inc. of Hangzhou, with the model number JXK-013;
and/or the time of ultrasonic dispersion is 1 hour.
4. A modified conductive powder obtained by the method for producing a modified conductive powder according to any one of claims 1 to 3.
5. The conductive master batch is characterized by comprising the following components: the modified conductive powder according to claim 4, a dispersant and a polymer matrix;
wherein the addition amount of the modified conductive powder is 40-60 wt%, for example 50 wt%; the addition amount of the dispersant is 1 wt% to 3 wt%, for example, 2 wt%; the addition amount of the modified conductive powder refers to the mass percentage of the modified conductive powder in the total mass of the polymer matrix and the modified conductive powder; the addition amount of the dispersing agent is the percentage of the mass of the dispersing agent in the total mass of the polymer matrix and the modified conductive powder.
6. The conductive masterbatch of claim 5 wherein the dispersant is a polyester wax; preferably, the polyester wax is commercially available from Shanghai Kahn chemical Co., Ltd, model No. WE 4;
and/or, the conductive master batch also comprises an antioxidant; preferably, the antioxidant is added in an amount of 0.2 wt% to1 wt%, for example, 0.5 wt%;
and/or, the conductive master batch also comprises a delustering agent; preferably, the addition amount of the matting agent is 1 wt% to 5 wt%, for example, 2 wt%;
and/or the polymer matrix is a polyester polymer matrix or a polyamide polymer matrix;
and/or the polymer matrix is powder, such as PET powder or PA6 powder;
and/or the polymeric matrix is dried prior to use.
7. The conductive masterbatch of claim 6, wherein the antioxidant is 1010 antioxidant or DLTP antioxidant; preferably, the 1010 antioxidant is commercially available from Shanghai Lier New materials, Inc. under the model LENOX 1010; the DLTP antioxidant is commercially available from Nanjing Pasteur chemical Co., Ltd, and has the model of BSD-DLTP;
and/or the flatting agent is one or more of titanium dioxide, silicon dioxide and zinc oxide; preferably, the titanium dioxide is commercially available from Nanjing titanium dioxide chemical Co., Ltd, model No. NR 930; the silica is commercially available from degussa chemical ltd under the model number R974; the zinc oxide is commercially available from Bofu science and technology and has the model number of S40;
and/or the polyester polymer matrix is PET, PBT or PTT; preferably PET; more preferably, the PET is commercially available from Shanghai distance spinning, has a model number of CB602 and a viscosity of 0.8 dL/g;
and/or the polyamide polymer matrix is PA6 or PA 66; preferably PA 6; more preferably, the PA6 is commercially available from Zhejiang golden color New materials, Inc., with a model number of M2400 and a viscosity of 2.47 dL/g;
and/or the drying temperature of the polymer matrix of the conductive master batch is 80-140 ℃, such as 90 ℃, 100 ℃ or 120 ℃;
and/or the drying time of the polymer matrix of the conductive master batch is 4-12 hours, such as 4 hours, 6 hours or 8 hours.
8. The preparation method of the conductive master batch is characterized by comprising the following steps: mixing and extruding the components of the conductive master batch of any one of claims 5-7;
preferably, the extrusion is a twin-screw melt extrusion, and more preferably, the extrusion temperature is 200 to 270 ℃, for example, 240 to 270 ℃ or 200 to 230 ℃.
9. An electrically conductive fiber comprising the components: the conductive masterbatch according to any one of claims 5 to 7 and a polymer carrier; wherein the addition amount of the conductive master batch is 8-25 wt%; the addition amount of the conductive master batch is the percentage of the mass of the conductive master batch in the total mass of the conductive master batch and the polymer carrier;
preferably, the drying temperature of the polymer carrier is 90-140 ℃; and/or the drying time of the polymer carrier is 8-12 hours, such as 10 hours; and/or the polymer carrier is a polyester polymer carrier or a polyamide polymer carrier; and/or the polymer matrix and the polymer carrier are the same;
more preferably, the polymer carrier is PET, PBT or PTT; and/or the high molecular carrier is PA6 or PA 66;
more preferably, the polymer carrier is PET; and/or the polymer carrier is PA 6;
even more preferably, the PET is commercially available from Shanghai distance spinning, has a model number of CB602, and has a viscosity of 0.8 dL/g; and/or the PA6 is commercially available from Jincai New materials, Zhejiang, with a model number of M2400 and a viscosity of 2.47 dL/g.
10. A method for preparing conductive fibers is characterized by comprising the following steps: blending, melt spinning, the components of the conductive fiber of claim 9;
preferably, the polymer carrier is sliced and then blended with the conductive master batch; and/or the melt spinning is melt spinning by adopting a double-screw extruder; and/or the temperature of the melt spinning is 240-290 ℃; and/or the temperature of each heating cylinder body of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence or 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in sequence; and/or the melt spinning speed is 1000 to 3000m/min, such as 2000 m/min.
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