CN114685859B - 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

Info

Publication number
CN114685859B
CN114685859B CN202011635913.2A CN202011635913A CN114685859B CN 114685859 B CN114685859 B CN 114685859B CN 202011635913 A CN202011635913 A CN 202011635913A CN 114685859 B CN114685859 B CN 114685859B
Authority
CN
China
Prior art keywords
conductive
powder
master batch
polymer matrix
fiber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011635913.2A
Other languages
Chinese (zh)
Other versions
CN114685859A (en
Inventor
唐晓峰
池玉玲
余子涯
逯琪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Langyi Functional Materials Co ltd
Original Assignee
Shanghai Langyi Functional Materials Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Langyi Functional Materials Co ltd filed Critical Shanghai Langyi Functional Materials Co ltd
Priority to CN202011635913.2A priority Critical patent/CN114685859B/en
Publication of CN114685859A publication Critical patent/CN114685859A/en
Application granted granted Critical
Publication of CN114685859B publication Critical patent/CN114685859B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

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 batches and a 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 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 is a fiber having a surface resistance of 10 under standard conditions (20 ℃ C., 65% relative humidity) 7 And omega cm or less. The conductive fiber has good charge transmission capability, can eliminate static in extremely short time, and is beneficial to processing and using of fiber products. In addition to antistatic propertiesIn addition, the conductive fiber fabric also has the functions of conducting electricity, shielding electromagnetic waves and the like, and has wide application prospects in the aspects of intelligent wearable textiles, flexible electromagnetic shielding nets and the like.
Currently, conductive fibers can be classified into:
1) Conductive fibers of uniform composition, such as metal conductive fibers and carbon fibers. When the metal conductive fiber is used as a fabric, the hand feeling is poor, the cohesion is difficult, and the fabric cannot be dyed. The carbon fiber has low elongation at break, is difficult to process, and is black, so that the application of the carbon fiber is limited.
2) Coated conductive fiber: the conductivity of the fiber is related to the thickness and compactness of the surface conductive layer, and the conductive network of the surface is damaged to a certain extent due to the fact that the conductive layer is arranged on the surface of the fiber, washing, friction, acid/alkali conditions and the like, so that the conductivity of the fiber is poor. For example, chinese patent CN1584140a discloses a method for preparing conductive fiber by coating conductive carbon black as a conductive component, dispersing it in polyester by dispersion treatment, extruding to obtain conductive masterbatch, and then spinning. The conductive fiber is black in color, is not easy to dye, and has poor spinnability at high content.
3) Blend type conductive fiber: conductive fillers are dispersed in a polymer matrix and made into conductive fibers by solvent or melt spinning processes. The conductivity of the blend type conductive fiber depends on the content of filler, the dispersion effect, the processing method, the type of the blend type conductive fiber and the polymer matrix, etc. The conductive filler in the fiber is uniformly dispersed in the inside and the surface of the fiber, so that the fiber has excellent conductive durability. Is the preparation method of the conductive fiber with the most extensive application range at present.
Disclosure of Invention
The invention aims to overcome the defects of poor dispersibility and functionality of conductive powder and higher color and resistivity of the prepared conventional conductive fiber in the prior art, and provides a modified conductive powder, conductive master batch, conductive fiber and a preparation method thereof.
The technical problems are solved by the following technical scheme.
The invention provides a preparation method of modified conductive powder, which comprises the following steps: reacting the metal oxide conductive powder with the mixed aqueous solution of the compatilizer, and drying to obtain the metal oxide conductive powder;
wherein the compatibilizing agent is added in an amount of 0.5wt% to 5wt%, for example 2wt%; the addition amount of the compatilizer refers to the mass percentage of the compatilizer to the conductive powder; the temperature of the reaction is 50 to 80 ℃, for example 65 ℃.
In the present invention, the metal oxide conductive powder may be conventional in the art; preferably one or more of antimony doped tin oxide (ATO), aluminum doped zinc oxide (AZO) and tin doped indium oxide (ITO).
Preferably, the antimony doped tin oxide (ATO) is commercially available from New Material Co., ltd., type BY-TO1, particle size 100nm-200nm.
Preferably, the aluminum-doped zinc oxide (AZO) is commercially available from Xuancheng Jinrui New Material Co., ltd, and has a model of JR-AZO and a particle size of 200-300nm.
Preferably, the tin doped indium oxide (ITO) is commercially available from Anhui Ke Run nanotechnology Co., ltd., model KR-ITO, particle size 300nm.
In the present invention, the particle size of the metal oxide conductive powder may be conventional in the art; preferably 100 to 500nm.
In the present invention, the compatibilizing agent may be conventional in the art, and generally refers to a material capable of improving 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 new materials of Nanjun, model KH560; the titanate coupling agent is commercially available from Nanjing Tencean chemical industry Co., ltd, and the model is JTW-131; the aluminate coupling agent is commercially available from jekca technology limited, hangzhou under the model number JXK-013.
In the present invention, those skilled in the art know that the metal oxide conductive powder is uniformly mixed with the compatibilizer by ultrasonic dispersion.
Wherein, preferably, the time of ultrasonic dispersion is 1 hour.
In the present invention, the time of the reaction may be conventional in the art; preferably 3 to 6 hours, for example 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 present 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 ultrasonic dispersion time is 1 hour, the volume of water in the mixed aqueous solution is 500mL, the reaction time is 3 hours, the reaction temperature is 50 ℃, and the drying is that after filtration and washing, the drying is performed.
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 compatilizer is a titanate coupling agent, the addition amount of the compatilizer is 0.4g, the ultrasonic dispersion time is 1 hour, the volume of water in the mixed aqueous solution is 500mL, the reaction time is 4.5 hours, the reaction temperature is 65 ℃, and the drying is that after filtration and washing, the drying is performed.
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 compatilizer is an aluminate coupling agent, the addition amount of the compatilizer is 1.5g, the ultrasonic dispersion time is 1 hour, the volume of water in the mixed aqueous solution is 500mL, the reaction time is 6 hours, the reaction temperature is 80 ℃, and the drying is that after filtration and washing, the drying is performed.
The invention provides a 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 dispersing agent and the polymer matrix;
wherein the addition amount of the modified conductive powder is 40-60 wt%, such as 50wt%; the dispersant is added in an amount of 1wt% to 3wt%, for example, 2wt%; the addition amount of the modified conductive powder refers to the percentage of the mass of the modified conductive powder to the total mass of the polymer matrix and the modified conductive powder; the addition amount of the dispersing agent refers to the mass percentage of the dispersing agent in the total mass of the polymer matrix and the modified conductive powder.
In the invention, the dispersing agent can be conventional in the art, and generally refers to a functional auxiliary agent capable of promoting the dispersion of the modified conductive powder in the polymer matrix; preferably polyester wax; more preferably, the polyester wax is commercially available from Shanghai Kaiyin chemical Co., ltd., model number WE4.
Preferably, the conductive master batch further comprises an antioxidant; more preferably, the antioxidant is added in an amount of 0.2wt% to 1wt%, for example, 0.5wt%.
Wherein, the antioxidant can be conventional in the art and generally refers to an auxiliary agent capable of reducing oxidative degradation of a polymer; preferably 1010 antioxidant or DLTP antioxidant; more preferably, the 1010 antioxidant is commercially available from Shanghai Lier New Material Co., ltd., model LENOX 1010; the DLTP antioxidant is commercially available from Nanjing Baside chemical industry Co., ltd, model number BSD-DLTP.
Preferably, the conductive master batch further comprises a matting agent; more preferably, the matting agent is added in an amount of 1 to 5wt%, for example, 2wt%.
Wherein, the matting agent can be a conventional matting agent, and generally refers to nanoscale powder capable of improving the visible light scattering capacity 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 number NR930; the silica is commercially available from Desoxhlet chemical Co., ltd, model R974; the zinc oxide is commercially available from Bofu technology, model number S40.
The addition amount in the invention refers to the percentage of the mass of the antioxidant or the matting agent to 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, type CB602, having a viscosity of 0.8dL/g.
Wherein the polyamide-based polymer matrix may be conventional in the art, such as PA6, PA66; preferably PA6; more preferably, the PA6 is commercially available from Zhejiang gold New Material Co., ltd, model M2400, viscosity 2.47dL/g.
Preferably, the polymer matrix is in the form of powder, such as PET powder or PA6 powder.
In the present invention, those skilled in the art know that the polymer matrix needs to be dried before use, and the drying operation of the polymer matrix may be conventional in the art.
Preferably, the temperature of drying the polymer matrix of the conductive masterbatch is 80 to 140 ℃, for example 90 ℃, 100 ℃ or 120 ℃.
Preferably, the polymeric matrix of the conductive masterbatch is dried for a period of time ranging from 4 to 12 hours, for example, 4 hours, 6 hours or 8 hours.
The invention provides a preparation method of a conductive master batch, which comprises the following steps: mixing the components of the conductive master batch, and extruding.
In the present invention, the extrusion is generally carried out by twin-screw melt extrusion at a temperature of 200 to 270℃such as 240 to 270℃or 200 to 230℃as known to those skilled in the art.
In one embodiment of the present invention, the polymer matrix is PET powder, the polymer matrix is added in an amount of 240g, the polymer matrix is dried at 140 ℃, the polymer matrix is dried for 4 hours, the modified conductive powder is added in an amount of 160g, the antioxidant is 1010 antioxidant, the antioxidant is added in an amount of 0.48g, the dispersant is a polyester wax dispersant, the dispersant is added in an amount of 2.4g, the matting agent is titanium dioxide, the matting agent is added in an amount of 2.4g, the conductive masterbatch is extruded by the twin screw extruder, and the extrusion temperature is 240 to 270 ℃.
In another embodiment of the present invention, the polymer matrix is PET powder, the polymer matrix is added in an amount of 200g, the polymer matrix is dried at 120 ℃, the polymer matrix is dried for 6 hours, the modified conductive powder is added in an amount of 200g, the antioxidant is 1010 antioxidant, the antioxidant is added in an amount of 1g, the dispersant is a polyester wax dispersant, the dispersant is added in an amount of 4g, the matting agent is silica, the matting agent is added in an amount of 4g, the conductive masterbatch is extruded by the twin screw extruder, and the extrusion temperature is 240 to 270 ℃.
In another embodiment of the present invention, the polymer matrix is PET powder, the polymer matrix is added in an amount of 160g, the polymer matrix is dried at 100 ℃, the polymer matrix is dried for 8 hours, the modified conductive powder is added in an amount of 240g, the antioxidant is 1010 antioxidant, the antioxidant is added in an amount of 1.6g, the dispersant is a polyester wax dispersant, the dispersant is added in an amount of 4.8g, the matting agent is zinc oxide, the matting agent is added in an amount of 8g, the conductive masterbatch is extruded by the twin screw extruder, and the extrusion temperature is 240 to 270 ℃.
In another embodiment of the present invention, the polymer matrix is PA6 powder, the polymer matrix is added in an amount of 240g, the polymer matrix is dried at 80 ℃, the polymer matrix is dried for 8 hours, the modified conductive powder is added in an amount of 160g, the antioxidant is DLTP antioxidant, the antioxidant is added in an amount of 0.48g, the dispersant is a polyester wax dispersant, the dispersant is added in an amount of 2.4g, the matting agent is titanium dioxide, the matting agent is added in an amount of 2.4g, the conductive masterbatch is extruded by the twin screw extruder, and the extrusion temperature is 200 to 230 ℃.
In another embodiment of the present invention, the polymer matrix is PA6 powder, the polymer matrix is added in an amount of 200g, the polymer matrix is dried at 90 ℃, the polymer matrix is dried for 6 hours, the modified conductive powder is added in an amount of 200g, the antioxidant is 1010 antioxidant, the antioxidant is added in an amount of 1g, the dispersant is a polyester wax dispersant, the dispersant is added in an amount of 4g, the matting agent is silica, the matting agent is added in an amount of 4g, the conductive masterbatch is extruded by the twin screw extruder, and the extrusion temperature is 200 to 230 ℃.
In another embodiment of the present invention, the polymer matrix is PA6 powder, the polymer matrix is added in an amount of 160g, the polymer matrix is dried at 100 ℃, the polymer matrix is dried for 4 hours, the modified conductive powder is added in an amount of 240g, the antioxidant is 1010 antioxidant, the antioxidant is added in an amount of 1.6g, the dispersant is a polyester wax dispersant, the dispersant is added in an amount of 4.8g, the matting agent is zinc oxide, the matting agent is added in an amount of 8g, the conductive masterbatch is extruded by the twin screw extruder, and the extrusion temperature is 200 to 230 ℃.
The invention provides a conductive fiber, which comprises the following components: the conductive master batch and the macromolecule 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 to the total mass of the conductive master batch and the polymer carrier.
In the present invention, the polymeric carrier may be conventional in the art, and refers to a polymeric polymer capable of forming fibers; preferably a polyester-based polymer carrier or a polyamide-based 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, type CB602, having a viscosity of 0.8dL/g.
Wherein, the polyamide macromolecule carrier can be conventional in the art, such as PA6 and PA66; preferably PA6; more preferably, the PA6 is commercially available from Zhejiang gold New Material Co., ltd, model M2400, viscosity 2.47dL/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 polymeric carrier is dried for a period of 8 to 12 hours, for example 10 hours.
The invention provides a preparation method of conductive fibers, which comprises the following steps: blending the components of the conductive fiber and carrying out melt spinning.
Preferably, the polymeric carrier chip is blended with the conductive masterbatch.
In the present invention, the melt spinning may be performed conventionally in the art using a twin screw extruder.
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 sequence or 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in sequence.
In the present invention, the speed of the melt spinning may be conventional in the art; preferably 1000 to 3000m/min, for example 2000m/min.
In one embodiment of the present invention, the amount of the conductive masterbatch added is 100g, the polymer carrier is PET, the amount of the polymer carrier added 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 masterbatch, the mixture is melt-spun by a twin-screw extruder, the temperatures of the heating cylinders of the twin-screw extruder are 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the melt-spun speed is 1000m/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, the mixture is melt-spun by a twin-screw extruder, the temperature of each heating cylinder of the twin-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃, and the melt-spun speed is 2000m/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, the mixture is melt-spun by a twin-screw extruder, the temperature of each heating cylinder of the twin-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃, and the melt-spun speed is 3000m/min.
In another embodiment of the present invention, the addition amount of the conductive masterbatch is 100g, the polymer carrier is PA6, the addition amount of the polymer carrier is 400g, the drying temperature of the polymer carrier is 90 ℃, the drying time of the polymer carrier is 12 hours, the polymer carrier is sliced and then blended with the conductive masterbatch, the mixture is melt-spun by a twin-screw extruder, the temperatures of the heating cylinders of the twin-screw extruder are 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in sequence, and the melt-spun speed is 1000m/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, the mixture is melt-spun by a twin-screw extruder, the temperatures of the heating cylinders of the twin-screw extruder are 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in sequence, and the melt-spun speed is 2000m/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, the mixture is melt-spun by a twin-screw extruder, the temperatures of the heating cylinders of the twin-screw extruder are 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in sequence, and the melt-spun speed is 3000m/min.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
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 color and is easy to dye.
Drawings
Fig. 1 is a modified conductive powder prepared in example 1 of the present invention.
Fig. 2 is a 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 means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
In the following examples, the resistivity of the conductive fibers was measured by a fiber specific resistance tester under a humidity environment of 60wt% at a temperature of 25 ℃.
In the following examples, antimony doped tin oxide (ATO) was commercially available from New Material Co., ltd, beijing Boyu Gao, model BY-TO1, particle size 100nm-200nm; aluminum doped zinc oxide (AZO) is commercially available from Xuancheng Jinrui New Material Co., ltd, and has the model of JR-AZO and the particle size of 200-300nm; tin doped indium oxide (ITO) is commercially available from Anhui Kerun nanotechnology Co., ltd, model KR-ITO, particle size 300nm;
the silane coupling agent is commercially available from new materials of Nanjing Xuan, and the model is KH560; the titanate coupling agent is commercially available from Nanjing Tian Mian chemical industry Co., ltd, and the model is JTW-131; the aluminate coupling agent is commercially available from JieXK-013, hangzhou, jieXKa technology Co., ltd;
polyester wax is commercially available from Shanghai Kaijin chemical Co., ltd, model number WE4;
antioxidant 1010 is commercially available from Shanghai Lier New Material Co., ltd, model LENOX 1010; the antioxidant DLTP is commercially available from Nanjing Baside chemical industry Co., ltd, model number BSD-DLTP;
titanium dioxide is commercially available from Nanjing titanium dioxide chemical industry Co., ltd, model number NR930; silica is commercially available from Desoxhlet chemical Co., ltd, model R974; zinc oxide is commercially available from Bofu technology, model number S40;
PET is commercially available from Shanghai, model CB602, viscosity 0.8dL/g; PA6 is commercially available from Zhejiang golden Material New material Co., ltd, model M2400, viscosity 2.47dL/g.
Example 1
(1) Modified conductive powder
10g of ATO conductive powder is dispersed in 500mL of deionized water by 1 hour of ultrasonic, 0.05g of silane coupling agent KH560 is added, and the mixture is stirred and reacted for 3 hours at 50 ℃, filtered, washed and dried to obtain the modified conductive powder, as shown in figure 1.
(2) Conductive master batch
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 flatting agent are uniformly mixed, and then the twin-screw is regulated to perform blending extrusion at each temperature interval of 240-270 ℃ to obtain the conductive master batch, 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 body of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the melt spinning speed is 1000m/min; the conductive fiber is obtained as shown in fig. 3.
The resistivity of the conductive fiber was measured at 25℃and 60wt% using a fiber specific resistance tester and was 2.1X10% 5 Ωcm。
Comparative example 1
(1) Conductive master batch
240g of PET powder which is 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 flatting agent are uniformly mixed, and then blending extrusion is carried out by adjusting each temperature interval of a double screw at 240-270 ℃ 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 body of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the melt spinning speed is 1000m/min; thus obtaining the conductive fiber.
The resistivity of the conductive fiber was measured at 25℃and 60wt% using a fiber specific resistance tester and was 5.7X10 7 Ωcm。
Example 2
(1) Modified conductive powder
Dispersing 20g of ITO conductive powder in 500mL of deionized water by 1 hour of ultrasonic, 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 master batch
200g of PET powder which is dried at 120 ℃ for 6 hours, 200g of modified conductive powder, 1g of 1010 antioxidant, 4g of polyester wax dispersant and 4g of silicon dioxide flatting agent are uniformly mixed, and then the twin-screw is regulated to carry out blending extrusion at each temperature interval of 240-270 ℃ to obtain the conductive master batch.
(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 body of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the melt spinning speed is 2000m/min; thus obtaining the conductive fiber.
The resistivity of the conductive fiber was measured at 25℃and 60wt% using a fiber specific resistance tester and was 1.6X10 5 Ωcm。
Comparative example 2
(1) Modified conductive powder
Dispersing 20g of ITO conductive powder in 500mL of deionized water by 1 hour of ultrasonic, 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 master batch
200g of PET powder which is dried for 6 hours at 120 ℃, 200g of modified conductive powder, 1g of 1010 antioxidant and 4g of silicon dioxide flatting agent are uniformly mixed, and then the temperature ranges of the twin screws are regulated to be between 240 ℃ and 270 ℃ for blending extrusion, thus obtaining the conductive master batch.
(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 body of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the melt spinning speed is 2000m/min; thus obtaining the conductive fiber.
The resistivity of the conductive fiber was measured at 25℃and 60wt% using a fiber specific resistance tester and was 3.6X10 8 Ωcm。
Example 3
(1) Modified conductive powder
30g of AZO conductive powder is dispersed in 500mL of deionized water by 1 hour of ultrasonic, 1.5g of aluminate coupling agent is added, and the mixture is stirred and reacted for 6 hours at 80 ℃, filtered, washed and dried to obtain the modified conductive powder.
(2) Conductive master batch
160g of PET powder which is dried at 100 ℃ for 8 hours, 240g of modified conductive powder, 1.6g of 1010 antioxidant, 4.8g of polyester wax dispersant and 8g of zinc oxide matting agent are uniformly mixed, and then blending extrusion is carried out by adjusting each temperature interval of a double screw between 240 ℃ and 270 ℃ to obtain the conductive master batch.
(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 body of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the melt spinning speed is 3000m/min; thus obtaining the conductive fiber.
The resistivity of the conductive fiber was measured at 25℃and 60wt% using a fiber specific resistance tester and was 3.2X10 5 Ωcm。
Comparative example 3
(1) Conductive master batch
160g of PET powder which is dried for 8 hours at 100 ℃, 240g of AZO conductive powder, 1.6g of 1010 antioxidant and 8g of zinc oxide matting agent are uniformly mixed, and then the twin-screw is regulated to blend and extrude at the temperature of 240-270 ℃ to obtain the conductive master batch.
(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 body of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the melt spinning speed is 3000m/min; thus obtaining the conductive fiber.
The resistivity of the conductive fiber was measured at 25℃and 60wt% using a fiber specific resistance tester and was 7.6X10 8 Ωcm。
Example 4
(1) Modified conductive powder
Dispersing 10g of ATO conductive powder in 500mL of deionized water by 1 hour of ultrasonic, 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 master batch
240g of PA6 powder, 160g of modified conductive powder, 0.48g of DLTP antioxidant, 2.4g of polyester wax dispersant and 2.4g of titanium dioxide flatting agent which are dried at 80 ℃ for 8 hours are uniformly mixed, and then blending extrusion is carried out by adjusting each temperature interval of a double screw at 200-230 ℃ to obtain the conductive master batch.
(3) Conductive fiber
Uniformly mixing 100g of conductive master batch and 400g of PA6 slices dried for 12 hours at 90 ℃ and adopting a double-screw extruder for melt spinning; wherein, the temperature of each heating cylinder body of the double-screw extruder is 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in sequence, and the melt spinning speed is 1000m/min; thus obtaining the conductive fiber.
The resistivity of the conductive fiber was measured at 25℃and 60wt% using a fiber specific resistance tester and was 3.8X10 4 Ωcm。
Comparative example 4
(1) Conductive master batch
240g of PA6 powder, 160g of ATO conductive powder, 0.48g of DLTP antioxidant, 2.4g of polyester wax dispersant and 2.4g of titanium dioxide flatting agent which are dried at 80 ℃ for 8 hours are uniformly mixed, and then blending extrusion is carried out by adjusting each temperature interval of a double screw at 200-230 ℃ to obtain the conductive master batch.
(2) Conductive fiber
Uniformly mixing 100g of conductive master batch and 400g of PA6 slices dried for 12 hours at 90 ℃ and adopting a double-screw extruder for melt spinning; wherein, the temperature of each heating cylinder body of the double-screw extruder is 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in sequence, and the melt spinning speed is 1000m/min; thus obtaining the conductive fiber.
The resistivity of the conductive fiber was measured at 25℃and 60wt% using a fiber specific resistance tester and was 3.5X10 7 Ωcm。
Example 5
(1) Modified conductive powder
Dispersing 20g of ITO conductive powder in 500mL of deionized water by 1 hour of ultrasonic, 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 master batch
200g of PA6 powder which is dried at 90 ℃ for 6 hours, 200g of modified conductive powder, 1g of 1010 antioxidant, 4g of polyester wax dispersant and 4g of silicon dioxide flatting agent are uniformly mixed, and then the twin-screw is regulated to carry out blending extrusion at each temperature interval of 200-230 ℃ to obtain the conductive master batch.
(3) Conductive fiber
Uniformly mixing 150g of conductive master batch and 350g of PA6 slices dried for 10 hours at 90 ℃ and adopting a double-screw extruder for melt spinning; wherein, the temperature of each heating cylinder body of the double-screw extruder is 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in sequence, and the melt spinning speed is 2000m/min; thus obtaining the conductive fiber.
The resistivity of the conductive fiber was measured at 25℃and 60wt% using a fiber specific resistance tester and was 4.2X10 4 Ωcm。
Comparative example 5
(1) Modified conductive powder
Dispersing 20g of ITO conductive powder in 500mL of deionized water by 1 hour of ultrasonic, 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 master batch
200g of PA6 powder, 200g of modified conductive powder, 1g of 1010 antioxidant and 4g of silicon dioxide flatting agent which are dried at 90 ℃ for 6 hours are uniformly mixed, and then the twin-screw is regulated to carry out blending extrusion at the temperature of 200-230 ℃ to obtain the conductive master batch.
(3) Conductive fiber
Uniformly mixing 150g of conductive master batch and 350g of PA6 slices dried for 10 hours at 90 ℃ and adopting a double-screw extruder for melt spinning; wherein, the temperature of each heating cylinder body of the double-screw extruder is 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in sequence, and the melt spinning speed is 2000m/min; thus obtaining the conductive fiber.
The resistivity of the conductive fiber was measured at 25℃and 60wt% using a fiber specific resistance tester and was 7.5X10 7 Ωcm。
Example 6
(1) Modified conductive powder
30g of AZO conductive powder is dispersed in 500mL of deionized water by 1 hour of ultrasonic, 1.5g of aluminate coupling agent is added, and the mixture is stirred and reacted for 6 hours at 80 ℃, filtered, washed and dried to obtain the modified conductive powder.
(2) Conductive master batch
160g of PA6 powder, 240g of modified conductive powder, 1.6g of 1010 antioxidant, 4.8g of polyester wax dispersant and 8g of zinc oxide matting agent which are dried at 100 ℃ for 4 hours are uniformly mixed, and then blending extrusion is carried out by adjusting each temperature interval of a double screw at 200-230 ℃ to obtain the conductive master batch.
(3) Conductive fiber
Uniformly mixing 208g of conductive master batch and 292g of PA6 slices dried for 8 hours at 90 ℃ and adopting a double-screw extruder for melt spinning; wherein, the temperature of each heating cylinder body of the double-screw extruder is 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in sequence, and the melt spinning speed is 3000m/min; thus obtaining the conductive fiber.
The resistivity of the conductive fiber was measured at 25℃and 60wt% using a fiber specific resistance tester and was 3.4X10 4 Ωcm。
Comparative example 6
(1) Conductive master batch
160g of PA6 powder, 240g of modified conductive powder, 1.6g of 1010 antioxidant and 8g of zinc oxide matting agent which are dried at 100 ℃ for 4 hours are uniformly mixed, and then the twin-screw is regulated to perform blending extrusion at the temperature of 200-230 ℃ to obtain the conductive master batch.
(2) Conductive fiber
Uniformly mixing 208g of conductive master batch and 292g of PA6 slices dried for 8 hours at 90 ℃ and adopting a double-screw extruder for melt spinning; wherein, the temperature of each heating cylinder body of the double-screw extruder is 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in sequence, and the melt spinning speed is 3000m/min; thus obtaining the conductive fiber.
The resistivity of the conductive fiber was measured at 25℃and 60wt% using a fiber specific resistance tester and was 5.9X10 8 Ωcm。
Comparative example 7
(1) Modified conductive powder
Dispersing 10g of ATO conductive powder in 500mL of deionized water by 1 hour of ultrasonic, 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 master batch
240g of PET powder which is 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 flatting agent are uniformly mixed, and then blending extrusion is carried out by adjusting each temperature interval of a double screw at 240-270 ℃ 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 body of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the melt spinning speed is 1000m/min; thus obtaining the conductive fiber.
The resistivity of the conductive fiber was measured at 25℃and 60wt% using a fiber specific resistance tester and was 2.5X10 9 Ωcm。
Comparative example 8
(1) Modified conductive powder
Dispersing 20g of ITO conductive powder in 500mL of deionized water by 1 hour of ultrasonic, 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 master batch
200g of PET powder which is dried at 120 ℃ for 6 hours, 200g of modified conductive powder, 1g of 1010 antioxidant, 4g of polyester wax dispersant and 4g of silicon dioxide flatting agent are uniformly mixed, and then the twin-screw is regulated to carry out blending extrusion at each temperature interval of 240-270 ℃ to obtain the conductive master batch.
(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 body of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the melt spinning speed is 2000m/min; thus obtaining the conductive fiber.
The resistivity of the conductive fiber was measured at 25℃and 60wt% using a fiber specific resistance tester and was 3.7X10 9 Ωcm。
Comparative example 9
(1) Modified conductive powder
30g of AZO conductive powder is dispersed in 500mL of deionized water by 1 hour of ultrasonic, 1.5g of aluminate coupling agent is added, and the mixture is stirred and reacted for 6 hours at room temperature, filtered, washed and dried to obtain the modified conductive powder.
(2) Conductive master batch
160g of PET powder which is dried at 100 ℃ for 8 hours, 240g of modified conductive powder, 1.6g of 1010 antioxidant, 4.8g of polyester wax dispersant and 8g of zinc oxide matting agent are uniformly mixed, and then blending extrusion is carried out by adjusting each temperature interval of a double screw between 240 ℃ and 270 ℃ to obtain the conductive master batch.
(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 body of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the melt spinning speed is 3000m/min; thus obtaining the conductive fiber.
The resistivity of the conductive fiber was measured at 25℃and 60wt% using a fiber specific resistance tester and was 5.6X10 8 Ωcm。
Comparative example 10
(1) Modified conductive powder
Dispersing 10g of ATO conductive powder in 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 master batch
240g of PET powder which is 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 flatting agent are uniformly mixed, and then blending extrusion is carried out by adjusting each temperature interval of a double screw at 240-270 ℃ 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 body of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ in sequence, and the melt spinning speed is 1000m/min; thus obtaining the conductive fiber.
The resistivity of the conductive fiber was measured at 25℃and 60wt% using a fiber specific resistance tester and was 5.4X10 9 Ωcm。
Effect example 1
The conductive fibers prepared in examples 1 to 6 and comparative examples 1 to 9 described above were subjected to color model tests, 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, a comprises colors ranging from dark green (low brightness value) to gray (medium brightness value) to bright pink (high brightness value); b is from bright blue (low luminance value) to gray (medium luminance value) to yellow (high luminance value). Thus, the value of b may represent the shade of the color of the resulting conductive fiber.
In addition, table 1 summarizes the specific resistance data of the conductive fibers prepared in examples 1 to 6 and comparative examples 1 to 10 described above.
TABLE 1
/>
As can be seen from Table 1, the conductive fibers prepared in examples 1 to 6 of the present invention were superior to those prepared in comparative examples 1 to 10 in terms of conductivity, and the conductive fibers prepared in examples 1 to 6 were lighter in color. In contrast, in comparative examples 1 and 4, in which the conductive powder was not modified, in which the dispersant was not added in comparative examples 2 and 5, in which the conductive powder was not modified in comparative examples 3 and 6, in which the dispersant was not added, in which the compatibilizer was too little in comparative example 7, in which the compatibilizer was too much in comparative example 8, and in comparative example 9, the conductive powder and the compatibilizer were reacted at room temperature, and in which acetone was used as a reaction system, in comparative example 10, the specific resistance of the resulting conductive fiber was increased and the color was darkened.

Claims (23)

1. The conductive master batch is characterized by comprising the following components: modified conductive powder, a dispersing agent and a polymer matrix;
the preparation method of the conductive powder comprises the following steps: reacting the metal oxide conductive powder with the mixed aqueous solution of the compatilizer, and drying to obtain the metal oxide 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 temperature of the reaction is 50-80 ℃;
the addition amount of the modified conductive powder is 40-60 wt%; the addition amount of the dispersing agent is 1-3 wt%; the addition amount of the modified conductive powder refers to the percentage of the mass of the modified conductive powder to the total mass of the polymer matrix and the modified conductive powder; the addition amount of the dispersing agent refers to the mass percentage of the dispersing agent in the total mass of the polymer matrix and the modified conductive powder.
2. The conductive masterbatch 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 2wt%;
and/or the compatilizer is one or more of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent;
and/or uniformly mixing the metal oxide conductive powder with the compatilizer by ultrasonic dispersion;
and/or the reaction time is 3-6 hours;
and/or, the temperature of the reaction is 65 ℃;
and/or the drying operation is that the filtering, washing and drying are carried out.
3. The conductive masterbatch of claim 2 wherein the reaction time is 4.5 hours.
4. The conductive masterbatch of claim 2 wherein the antimony doped tin oxide has a particle size of 100nm to 200nm;
and/or the particle size of the aluminum-doped zinc oxide is 200-300nm;
and/or the particle size of the tin-doped indium oxide is 300nm;
and/or the time of the ultrasonic dispersion is 1 hour.
5. The conductive masterbatch according to claim 1 wherein said dispersant is a polyester wax;
and/or, the conductive master batch further comprises an antioxidant;
and/or, the conductive master batch further comprises a matting agent;
and/or the polymer matrix is a polyester polymer matrix or a polyamide polymer matrix;
and/or the polymer matrix is in a powder shape;
and/or, the polymer matrix is dried before use.
6. The conductive masterbatch according to claim 5 wherein the antioxidant is added in an amount of 0.2wt% to 1wt%;
and/or the addition amount of the flatting agent is 1-5 wt%;
and/or the polymer matrix is PET powder or PA6 powder.
7. The conductive masterbatch according to claim 6 wherein said antioxidant is added in an amount of 0.5wt%;
and/or the addition amount of the matting agent is 2wt%.
8. The conductive masterbatch of claim 5 wherein the antioxidant is 1010 antioxidant or DLTP antioxidant;
and/or the delustrant is one or more of titanium dioxide, silicon dioxide and zinc oxide;
and/or the polyester polymer matrix is PET, PBT or PTT;
and/or the polyamide polymer matrix is PA6 or PA66;
and/or the drying temperature of the polymer matrix of the conductive master batch is 80-140 ℃;
and/or the drying time of the polymer matrix of the conductive master batch is 4-12 hours.
9. The conductive masterbatch according to claim 8 wherein said polyester-based polymeric matrix is PET;
and/or the polyamide polymer matrix is PA6;
and/or the drying temperature of the polymer matrix of the conductive master batch is 90 ℃, 100 ℃ or 120 ℃;
and/or the drying time of the polymer matrix of the conductive master batch is 4 hours, 6 hours or 8 hours.
10. The electrically conductive masterbatch of claim 9 wherein said PET has a viscosity of 0.8dL/g;
and/or, the viscosity of the PA6 is 2.47dL/g.
11. 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 according to any one of claims 1 to 10.
12. The method of producing a conductive masterbatch according to claim 11 wherein said extruding is by twin screw melt extrusion.
13. The method of producing a conductive masterbatch according to claim 12 wherein the extrusion temperature is 200-270 ℃.
14. The method of producing a conductive masterbatch according to claim 13 wherein the extrusion temperature is 240-270 ℃ or 200-230 ℃.
15. A conductive fiber, comprising the following components: the conductive masterbatch and the polymeric carrier of any one of claims 1-10; 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 to the total mass of the conductive master batch and the polymer carrier.
16. The conductive fiber of claim 15, wherein said polymeric support has a drying temperature of 90 to 140 ℃;
and/or the drying time of the polymer carrier is 8-12 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.
17. The conductive fiber of claim 16, wherein said polymeric support has a drying time of 10 hours.
18. The conductive fiber of claim 16, wherein said polymeric carrier is PET, PBT or PTT;
and/or the macromolecule carrier is PA6 or PA66.
19. The conductive fiber of claim 18, wherein said polymeric carrier is PET;
and/or the macromolecule carrier is PA6.
20. The conductive fiber of claim 19, wherein said PET has a viscosity of 0.8dL/g;
and/or, the viscosity of the PA6 is 2.47dL/g.
21. A method for preparing conductive fibers, comprising the steps of: blending and melt spinning the components of the conductive fiber according to any one of claims 15-20.
22. The method of producing a conductive fiber according to claim 21, wherein the polymer carrier is sliced and then blended with the conductive masterbatch;
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 of the double-screw extruder is 270 ℃, 275 ℃, 280 ℃ and 285 ℃ or 240 ℃, 250 ℃, 255 ℃ and 260 ℃ in sequence;
and/or the speed of the melt spinning is 1000-3000 m/min.
23. The method of producing conductive fibers of claim 22 wherein the melt spinning is at a speed of 2000m/min.
CN202011635913.2A 2020-12-31 2020-12-31 Modified conductive powder, conductive master batch, conductive fiber and preparation method thereof Active CN114685859B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011635913.2A CN114685859B (en) 2020-12-31 2020-12-31 Modified conductive powder, conductive master batch, conductive fiber and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011635913.2A CN114685859B (en) 2020-12-31 2020-12-31 Modified conductive powder, conductive master batch, conductive fiber and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114685859A CN114685859A (en) 2022-07-01
CN114685859B true CN114685859B (en) 2023-10-31

Family

ID=82135250

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011635913.2A Active CN114685859B (en) 2020-12-31 2020-12-31 Modified conductive powder, conductive master batch, conductive fiber and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114685859B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101085845A (en) * 2006-06-06 2007-12-12 中国石油化工股份有限公司 Conducting fibre master batch and preparation method thereof
CN104277435A (en) * 2014-09-23 2015-01-14 桐乡市中驰化纤有限公司 Black conductive electromagnetic shielding master batch for PET fiber and preparation method thereof
CN106065498A (en) * 2016-06-04 2016-11-02 江苏启弘新材料科技有限公司 The preparation method of antistatic fibre based on point discharge effect
CN107815743A (en) * 2017-10-31 2018-03-20 阜宁澳洋科技有限责任公司 Preparation method for the tin-antiomony oxide dispersion liquid of modified fibre electric conductivity, preparation method and conductive regenerated celulose fibre
CN110922762A (en) * 2019-10-23 2020-03-27 平湖阿莱德实业有限公司 High-conductivity silica gel composition based on conductive powder wet modification technology

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101085845A (en) * 2006-06-06 2007-12-12 中国石油化工股份有限公司 Conducting fibre master batch and preparation method thereof
CN104277435A (en) * 2014-09-23 2015-01-14 桐乡市中驰化纤有限公司 Black conductive electromagnetic shielding master batch for PET fiber and preparation method thereof
CN106065498A (en) * 2016-06-04 2016-11-02 江苏启弘新材料科技有限公司 The preparation method of antistatic fibre based on point discharge effect
CN107815743A (en) * 2017-10-31 2018-03-20 阜宁澳洋科技有限责任公司 Preparation method for the tin-antiomony oxide dispersion liquid of modified fibre electric conductivity, preparation method and conductive regenerated celulose fibre
CN110922762A (en) * 2019-10-23 2020-03-27 平湖阿莱德实业有限公司 High-conductivity silica gel composition based on conductive powder wet modification technology

Also Published As

Publication number Publication date
CN114685859A (en) 2022-07-01

Similar Documents

Publication Publication Date Title
US6184280B1 (en) Electrically conductive polymer composition
CN103554633B (en) A kind of High-voltage cable structure of excellent performance
CN106968026A (en) A kind of preparation method of graphene carbon black composite conducting fiber
CN108047569A (en) A kind of functional composite material and preparation method thereof
WO2012115344A1 (en) Electrically conductive polymer/filler composite, and method for preparing same
US8216492B2 (en) Conductive masterbatches and conductive monofilaments
CN105002595A (en) Polymer composite function fibers containing partial graphene, and preparation method thereof
CN101086088A (en) Conductive fiber and its preparation method
CN111363346A (en) Method for preparing antistatic black master batch by using graphene coated carbon black and product
CN101085845A (en) Conducting fibre master batch and preparation method thereof
CN114685859B (en) Modified conductive powder, conductive master batch, conductive fiber and preparation method thereof
CN108003612A (en) A kind of preparation method of the multifunctional composite with thermal conductivity electromagnetic shielding
CN1268792C (en) High-efficient conductive fibre and preparing method thereof
CN109722022A (en) A kind of novel extrusion, blow molding grade glass fiber reinforced nylon material and preparation method thereof
CN101158058A (en) Conductive fibre
CN100478392C (en) High-temperature-resisting thermosensitive resistance composite material and its production
CN101747597B (en) Conductive batch and conductive single fiber
CN101844377B (en) Preparation method of conductive master batches
CN111849142A (en) Semiconductive PC black master batch and preparation method thereof
CN103668543A (en) Carbon-based high molecular polymeric conductive fiber and preparation method thereof
CN1211507C (en) Conductive fiber and preparing method
CN113957705B (en) Preparation method of conductive fabric
CN107815743A (en) Preparation method for the tin-antiomony oxide dispersion liquid of modified fibre electric conductivity, preparation method and conductive regenerated celulose fibre
CN112921427B (en) Modified titanium dioxide nanotube, conductive master batch and fiber, preparation method and application
CN115232336B (en) Heating film material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant